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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

INVESTIGATION OF ROCK-FLUID INTERACTIONS USING GEOMATERIAL MICROFLUIDICS

Illite and Illite-Smectite clays are reportedly the Caney Shale's most prevalent clay minerals. The swelling and fines migration of clays may occur when water-based fluids contact the clay minerals. This may result in the reduction of pore space and permeability, and wettability alteration. Therefore, we quantified the swelling potentials, fines migration and wettability alteration of Illite and Illite-Smectite clays upon exposure to model brines and a produced water, and a model oil and a crude oil. We measured density, viscosity, pH, TDS, and interfacial tension as they are important in multiphase flow and displacement characteristics. Geomaterial microfluidics is recently being used to study physicochemical interactions of solid-fluid systems. It facilitates visualizing the surface behavior upon exposure to various fluids. This study includes preparation and characterization of Illite-Smectite clay-coated glass capillary tubes. Illite and Illite-Smectite clay-coated geomaterial microfluidic surfaces were prepared to investigate the effects of first contact fluid, brine salinity, and aging on wettability. In this work, advancing and receding contact angles of model brine-air, model oil-air, produced water-air, crude oil-air, model brine-model oil systems, and produced water-crude oil systems have been measured in the untreated, and clay-coated microfluidic channels of 1000 µm width and 50 µm depth. The aging effect was studied by retaining the non-aqueous and aqueous solutions in the corresponding microfluidic channels for approximately 24 h in the case of channels first contacted by aqueous and non-aqueous solutions, respectively. The advancing and receding contact angles of Caney shale-crude oil-produced water systems were also measured. The experimental findings indicate the swelling potential, fines migration, and wettability alteration of Illite and Illite-Smectite clays. The results signify the influence of first contact fluid, brine salinity, and aging on wettability of the untreated and clay-coated microfluidic surfaces. The experiments also demonstrate the wetting nature of the Caney shale samples from reservoir and non-reservoir zones.

02 PETROLEUM↗
NASA NTRS1992

Applications for special-purpose minerals at a lunar base

Maintaining a colony on the Moon will require the use of lunar resources to reduce the number of launches necessary to transport goods from the Earth. It may be possible to alter lunar materials to produce minerals or other materials that can be used for applications in life support systems at a lunar base. For example, mild hydrothermal alteration of lunar basaltic glasses can produce special-purpose minerals (e.g., zeolites, smectites, and tobermorites) that in turn may be used in life support, construction, waste renovation, and chemical processes. Zeolites, smectites, and tobermorites have a number of potential applications at a lunar base. Zeolites are hydrated aluminosilicates of alkali and alkaline earth cations that possess infinite, three-dimensional crystal structures. They are further characterized by an ability to hydrate and dehydrate reversibly and to exchange some of their constituent cations, both without major change of structure. Based on their unique absorption, cation exchange, molecular sieving, and catalytic properties, zeolites may be used as a solid support medium for the growth of plants, as an adsorption medium for separation of various gases (e.g., N2 from O2), as catalysts, as molecular sieves, and as a cation exchanger in sewage-effluent treatment, in radioactive waste disposal, and in pollution control. Smectites are crystalline, hydrated 2:1 layered aluminosilicates that also have the ability to exchange some of their constituent cations. Like zeolites, smectites may be used as an adsorption medium for waste renovation, as adsorption sites for important essential plant growth cations in solid support plant growth mediums (i.e., 'soils'), as cation exchangers, and in other important application. Tobermorites are cystalline, hydrated single-chained layered silicates that have cation-exchange and selectivity properties between those of smectites and most zeolites. Tobermorites may be used as a cement in building lunar base structures, as catalysts, as media for nuclear and hazardous waste disposal, as exchange media for waste-water treatment, and in other potential applications. Special-purpose minerals synthesized at a lunar base may also have important applications at a space station and for other planetary missions. New technologies will be required at a lunar base to develop life support systems that are self-sufficient, and the use of special-purpose minerals may help achieve this self-sufficiency.

Ming, Douglas W.↗
NASA NTRS2004

Precipitation of Secondary Phases from the Dissolution of Silicate Glasses

Basaltic and anorthositic glasses were subjected to aqueous weathering conditions in the laboratory where the variables were pH, temperature, glass composition, solution composition, and time. Leached layers formed at the surfaces of glasses followed by the precipitation of X-ray amorphous iron and titanium oxides in acidic and neutral solutions at 25 C over time. Glass under oxidative hydrothermal treatments at 150 C yielded a three-layered surface; which included an outer smectite layer, a Fe-Ti oxide layer and an innermost thin leached layer. The introduction of Mg into solutions facilitated the formation of phyllosilicates. Aqueous hydrothermal treatment of anorthositic glasses (high Ca, low Ti) at 200 C readily formed smectite, whereas, the basaltic glasses (high Ti) were more resistant to alteration and smectite was not observed. Alkaline hydrothermal treatment at 2000e produced zeolites and smectites; only smectites formed at 200 C in neutral solutions. These mineralogical changes, although observed under controlled conditions, have direct applications in interpreting planetary (e.g., meteorite parent bodies) and terrestrial aqueous alteration processes.

Ming, Douglas W.↗
NASA NTRS2016

Localized and Areally Extensive Alterations in Marathon Valley, Endeavour Crater Rim, Mars

Mars Exploration Rover Opportunity is exploring the rim of 22 km diameter, Noachian-aged Endeavour crater. Marathon Valley cuts through the central region of the western rim providing a window into the local lower rim stratigraphic record. Spectra from the Compact Reconnaissance Imaging Spectrometer for Mars show evidence for the occurrence of Fe-Mg smectite in this valley, indicating areally extensive and distinct lithologic units and/or styles of aqueous alteration. The Alpha Particle X-ray Spectrometer has determined the compositions of 59 outcrop targets on untreated, brushed and abraded surfaces. Rocks in the Marathon Valley region are soft breccias composed of mm- to cm-sized darker clasts set in a lighter-toned, finegrained matrix. They are basaltic in non-volatile-element composition and compositionally similar to breccias investigated elsewhere on the rim. Alteration styles recorded in the rocks include: (1) Enrichments in Si, Al, Ti and Cr in more reddish-colored rock, consistent with leaching of more soluble cations and/or precipitation of Si +/- Al, Ti, Cr from fluids. Coprecipitation of Ge-rich phases with Si occurred in the western area only; high water:rock is indicated. Pancam multispectral observations indicate higher nanophase ferric oxide contents, but the rocks have lower Fe contents. The highly localized nature of the red zones indicate they cannot be the source of the widespread smectite signature observed from orbit. (2) Outcrops separated by approximately 65 m show common compositional changes between brushed and abraded (approximately 1 mm deep) targets: increases in S and Mg; decreases in Al, Cl and Ca. These changes are likely due to relatively recent, surface-related alteration of valley rocks and formation of surface coatings under low water:rock. (3) One target, from the center of a region of strong CRISM smectite signature, shows modest differences in composition (higher Si, K; lower Mn) compared to most Marathon Valley rocks, while another target approximately 40 cm away on the same outcrop does not; a change towards smectite bulk compositions is not observed. The smectite signature likely resulted from alteration under low water:rock such that primary minerals were partially altered to phyllosilicates, but wholesale leaching of cations by fluids did not occur.

Mittlefehldt, David W.↗
NASA NTRS2020

Automated Identification and Differentiation of Spectrally Similar Hydrothermal Minerals on Mars

Early telescopic observations corroborated hydration related absorptions on Mars in the infrared. Images from the Viking missions led to speculation of hydrothermal alteration and were followed by two missions which mapped the spatial variability of the ~ 3 μm hydration feature. Since then, the Compact Reconnaissance Imager for Mars (CRISM) has provided high spatial resolution (up to 18m) spectral identification of a suite of hydrothermal and diagenetic minerals which have illuminated a range of formation mechanisms. Presence/absence and spatial segregation or mixing of minerals like prehnite, epidote, chlorite amphiboles, and mixed-layer Fe/Mg smectite-chlorite provide valuable evidence for the geologic setting of deposits on Earth, and these phases are often used as temperature and aqueous chemistry indicators in terrestrial systems. Mapping the distribution of these phases will help to answer whether Mars had widespread conditions favorable for low-grade metamorphism and diagenesis, or only focused hydrothermal systems in areas of high heat flow. Further characterizing the chemistry and structure of these phases will then help to answer how most of the widespread Fe/Mg phyllosilicates formed, further defining early geochemical cycling and climate. A fully automated approach for accurate mapping of important hydrothermal mineral phases on Mars has been a challenge. Due to overlapping features in the M-OH region (~2.2-2.4 μm), the strongest absorption features of chlorite, prehnite, and epidote in the short-wave infrared are difficult to distinguish from one another and from the most commonly occurring hydrated silicates on Mars, Fe/Mg smectites. Weaker absorptions are present in both prehnite and epidote which help to distinguish them from chlorite and smectites, but their relative strength in the presence of noise and spatial mixing is often too low to confidently identify them without the noise suppression and feature enhancement methods described here. The spectral signatures of mixed-layer Fe/Mg smectite-chlorite and partially chloritized Fe/Mg smectites have not yet been adequately assessed. Here we evaluate the effectiveness of two empirical and statistical methods for identifying and differentiating these phases using CRISM data.

Rasmussen, B. P.↗
DOE OSTI2023

Chemistry and Dynamics of Supercritical Carbon Dioxide and Methane in the Slit Pores of Layered Silicates

In the mid 2010s, high-pressure diffraction and spectroscopic tools opened a window into the molecular-scale behavior of fluids at the conditions of many CO 2 sequestration and shale/tight gas reservoirs - conditions where CO 2 and CH 4 are present as variably wet supercritical fluids. Integrating high-pressure spectroscopy and diffraction with molecular modeling has revealed much about the ways that supercritical CO 2 and CH 4 behave in reservoir components, particularly in the slit-shaped micro- and meso-pores of layered silicates (phyllosilicates) abundant in caprocks and shales. This Account summarizes how supercritical CO 2 and CH 4 behave in the slit pores of swelling phyllosilicates as functions of the H 2 O activity, framework structural features, and charge-balancing cation properties at 90 bar and 323 K – conditions similar to a reservoir at ~1 km depth. Slit pores containing cations with large radii, low hydration energy, and large polarizability readily interact with CO 2 , allowing CO 2 and H 2 O to adsorb and co-exist in these interlayer pores over a wide range of fluid humidities. In contrast, cations with small radii, high hydration energy, and low polarizability weakly interact with CO 2 leading to reduced CO 2 uptake and a tendency to exclude CO 2 from interlayers when H 2 O is abundant. The reorientation dynamics of confined CO 2 depends on the interlayer pore height, which is strongly influenced by the cation properties, framework properties, and fluid humidity. The silicate structural framework also influences CO 2 uptake and behavior - for example, smectites with increasing F-for-OH substitution in the framework take up greater quantities of CO 2 . Reactions that trap CO 2 in carbonate phases have been observed in thin H 2 O films near smectite surfaces, including a dissolution-reprecipitation mechanism when the edge surface area is high and an ion exchange-precipitation mechanism when the interlayer cation can form a highly insoluble carbonate. In contrast, supercritical CH 4 does not readily associate with cations, does not react with smectites, and is only incorporated into interlayer slit mesopores when (i) the pore has a $z$-dimension large enough to accommodate CH 4 , (ii) the smectite has low charge and (iii) the H 2 O activity is low. In conclusion, the adsorption and displacement of CH 4 by CO 2 and vice-versa have been studied on the molecular scale in one shale, but opportunities remain to examine behavioral details in this more complicated, slit-pore inclusive system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

The Role of Clay in Limiting Frictional Healing in Fault Gouges

Abstract Frictional healing is fundamental to the seismic cycle and plays a role in the energy balance, dynamics, and recurrence interval of earthquakes and slow slip events. Although the healing behavior of quartz has been studied extensively, the role of clay content is less understood. We tested synthetic mixtures of quartz and smectite (10%–100% smectite) in a double‐direct shear configuration to measure frictional healing. We show that the magnitude and rate of healing decreases systematically with higher clay content (from 0.008/decade at 10% smectite to 0.002/decade at 100% smectite). Healing scales with both the magnitude of stress relaxation during holds and layer‐normal compaction of the gouge. We suggest this reflects the alignment of clay minerals, leading to saturation of the real area of contact that limits restrengthening during holds. The low healing rates of clay‐rich faults—together with rate‐neutral to rate‐strengthening friction—should promote frequent, small failures or stable sliding.

58 GEOSCIENCES↗
NASA NTRS2010

Evidence for Interlayer Collapse of Nontronite on Mars from Laboratory Visible and Near-IR Reflective Spectra

Dioctahedral smectites (e.g., nontronite and montmorillionite) are interpreted to occupy the optical surface of Mars at a number of locations on the basis of spectral features derived from interlayer H2O and MOH (M=Fe(3+)2, Fe(3+)Al, Al2, etc.) as observed by orbiting MRO-CRISM and MEx-OMEGA hyperspectral imaging spectrometers. At wavelengths shorter than approximately 2.7 micrometers, the strongest bands from interlayer H2O occur at approximately 1.4 and 1.9 micrometers from 2v1 and v1+v2, respectively, where v1 and v2 are the fundamental stretching and bending vibrations of the H2O molecule. Smectite MOH vibrations occur near 1.4 micrometers (stretching overtone) and in the region between 2.1 and 2.7 micrometers (stretching + bending combination). Because interlayer H2O can exchange with the martian environment, a number of studies have examined the strength of the interlayer H2O spectral features under Mars-like environmental conditions. The relationship between spectral properties and the underlying crystal structure of the smectites was not determined, and the extent of interlayer H2O removal was not established. We report combined visible and near-IR (VNIR), Mossbauer (MB), and powder X-ray diffraction (XRD) data for samples of the Fe-bearing smectite nontronite where the interlayer was collapsed by complete removal of interlayer H2O.

Morris, Richard V.↗
NASA NTRS2014

Griffith Saponite as an Analog for Clay Minerals at Yellowknife Bay in Gale Crater, Mars: A Marker for Low-temperature Hydrothermal Processes

The CheMin X-ray diffraction (XRD) instrument onboard the Mars Science Laboratory rover Curiosity in Gale Crater, Mars, discovered smectite in drill fines of the Sheepbed mudstone at Yellowknife Bay (YNB). The mudstone has a basaltic composition, and the XRD powder diffraction pattern shows smectite 02l diffraction bands peaking at 4.59 A for targets John Klein and Cumberland, consistent with tri-octahedral smectites (saponite). From thermal analysis, the saponite abundance is ~20 wt. %. Among terrestrial analogues we have studied, ferrian saponite from Griffith Park (Los Angeles, CA) gives the best match to the position of the 02l diffraction band of YNB saponites. Here we describe iron-rich saponites from a terrestrial perspective, with a focus on Griffith saponite, and discuss their implications for the mineralogy of Sheepbed saponite and its formation pathways. Iron-rich saponite: Iron-rich saponite on the Earth is recognized as a low-temperature (<100 C), authigenic alteration product of basalt [e.g., 4-16]. In the discussion that follows, we reference the position of the 02l band because it is a measure of the unit cell 'b' dimension of the octahedral layer and thus the cations (including Fe redox state) in the octahedral layer. Ordinarily, the 06l band near 1.5 A is used to determine the 'b' dimension of smectite, but this band is not accessible with MSL CheMin instrument. For reference, a ferrosaponite (i.e., Fe2+ saponite) studied by [15] has a 02l spacing of 4.72 A and Fe3+/Fe = 0.27 [15]. Samples of terrestrial ferrosaponite, however, are reported to oxidize on the timescale of days when removed from their natural environment and not protected from oxidation. The Griffith saponite is Mg-rich ferrian saponite, and sample AMNH 89172 has an 02l spacing of 4.59 A (same as the Sheepbed saponites) and Fe3+/Fe = 0.64 [3]. This similarity suggests that Sheepbed saponites are ferrian (incompletely oxidized ferrosaponite). More oxidized Griffith saponites (Fe3+/Fe > 0.90) have somewhat smaller 02l d-spacings and also show Mossbauer evidence for an XRD amorphous Fe-bearing phase (e.g., ferrihydrite, hisingerite, superparamagnetic ferric oxides, etc.). The Griffith saponite occurs as vesicle fills, as replacements of olivine, and as replacements of mesostasis (basaltic glass). Similar occurrence modes are reported elsewhere. Hisingerite has been proposed by [13] as the alteration product of ferrian saponite whose precursor by oxidation was ferrosaponite.

Morris, R.V.↗
NASA NTRS2014

Mineralogy of Fluvio-Lacustrine Sediments Investigated by Curiosity During the Prime Mission: Implications for Diagenesis

The Mars Science Laboratory rover Curiosity investigated sedimentary rocks that were deposited in a diversity of fluvio-lacustrine settings. The entire science payload was employed to characterize the mineralogy and chemistry of the Sheepbed mudstone at Yellowknife Bay and the Windjana sandstone at the Kimberley. Data from the CheMin instrument, a transmission Xray diffractometer, were used to determine the quantitative mineralogy of both samples. The Sheepbed mudstone contains detrital basaltic minerals, calcium sulfates, iron oxides or hydroxides, iron sulfides, trioctahedral smectite, and amorphous material. The mineral assemblage and chemical data from APXS suggest that the trioctahedral smectite and magnetite formed authigenically as a result of alteration of olivine. The apparent lack of higher-grade phyllosilicates (e.g., illite and chlorite) and the presence of anhydrite indicate diagenesis at ~50- 80 ºC. The mineralogy of the Windjana sandstone is different than the Sheepbed mudstone. Windjana contains significant abundances of K-feldspar, low- and high-Ca pyroxenes, magnetite, phyllosilicates, and amorphous material. At least two distinct phyllosilicate phases exist: a 10 Å phase and a component that is expanded with a peak at ~11.8 Å. The identity of the expanded phase is currently unknown, but could be a smectite with interlayer H2O, and the 10 Å phase could be illite or collapsed smectite. Further work is necessary to characterize the phyllosilicates, but the presence of illite could suggest that Windjana experienced burial diagenesis. Candidates for the cementing agents include fine-grained phyllosilicates, Fe-oxides, and/or amorphous material. Interpretations of CheMin data from the Windjana sandstone are ongoing at the time of writing, but we will present an estimate of the composition of the amorphous material from mass balance calculations using the APXS bulk chemistry and quantitative mineralogy from CheMin.

Rampe, Elizabeth B.↗
NASA NTRS2016

Multispectral VNIR Observations by the Opportunity Rover Pancam of Multiple Episodes of Aqueous Alteration in Marathon Valley, Endeavour Crater, Mars

Since early 2015, the Mars Exploration Rover Opportunity has been exploring the break in the rim of Endeavour Crater dubbed Marathon Valley by the rover team. Marathon Valley was identified by orbital hyperspectral data from the MRO CRISM as having a relatively strong spectral feature in the 2.3 micrometer region indicative of an Mg or Fe-OH combination overtone absorption band indicative of smectite clay. Earlier in its mission, Opportunity examined the Matijevic Hill region on the more northerly Cape York crater rim segment and found evidence for smectite clays in a stratigraphically lower, pre-impact formed unit dubbed the Matijevic formation. However, the smectite exposures in Marathon Valley appear to be associated with the stratigraphically higher Shoemaker formation impact breccia. Evidence for alteration in this unit in Marathon Valley is provided by Pancam multispectral observations in the 430 to 1010 nm visible/near infrared (VNIR) spectral range. Sinuous troughs ("red zones") contain fragmented cobbles and pebbles displaying higher blue-to-red slopes, moderately higher 535 nm band depths, elevated 754 to 934 nm, and negative 934 to 1009 nm slopes. The lack of an absorption at 864 to 904 nm indicates the lack of crystalline red hematite in these red zones, but likely an enrichment in nanophase ferric oxides. The negative 934 to 1009 nm slope is potentially indicative of the presence of adsorbed or structurally bound water. A scuff in a red zone near the southern wall of Marathon Valley uncovered light-toned soils and a pebble with an 803 to 864 nm absorption resembling that of light-toned Fe-sulfate bearing soils uncovered by the Spirit rover in the Columbia Hills of Gusev crater. APXS chemical measurements indicated enrichments of Mg and S in the scuff soils and the pebble, Joseph Field, with the strongest 803 nm band- consistent with Mg and Fe sulfates. The presence of Fe and Mg sulfates can be interpreted as evidence of a potentially later episode of aqueous alteration with an earlier, neutral to alkaline pH episode forming the Fe/Mg smectites and a later acid pH episode forming the Fe and Mg sulfates.

Farrand, William H.↗
NASA NTRS2019

Saponite Dissolution Experiments and Implications for Mars

Recent work suggests that the mineralogical sequence of the Murray formation at Gale crater may have resulted from diagenetic alteration after sedimentation, or deposition in a stratified lake with oxic surface and anoxic bottom waters. Fe-containing clay minerals are common both at Gale crater, and throughout the Noachian-aged terrains on Mars. These clay minerals are primarily ferric (Fe3+), and previous work suggests that these ferric clay minerals may result from alteration of ferrous (Fe2+) smectites that were oxidized after deposition. The detection of trioctahedral smectites at Gale crater by CheMin suggests Fe2+ smectite was also deposited during the early Hesperian. However, due to their sensitivity to oxygen, Fe2+ smectites are difficult to analyze on Earth and very few saponite dissolution rates exist in the literature. To the best of our knowledge, no experiments have measured the dissolution rates of ferrous saponites under oxidizing and reducing conditions. In order to better understand the characteristics of water-rock interaction at Gale crater, particularly the oxidation state, we report our results to date on ongoing syntheses of ferrous and magnesium saponites and dissolution experiments of natural saponite under ambient conditions. Future experiments will include the dissolution of synthetic ferric, ferrous, and magnesium saponites under oxidizing and anoxic conditions at a range of pH values.

Luu, N. C.↗
NASA NTRS2020

Saponite Dissolution Experiments and Implications for Mars

Phyllosilicates detected throughout the Noachian terrains of Mars provide ample evidence of water-rock interactions in its geologic past, and characterizing their formation would elucidate past environmental conditions on the martian surface. Previous work suggests that ferric smectite may have been deposited in the Noachian as ferroan (Fe2+) smectite and then subsequently oxidized after formation. This is further supported by the detection of trioctahedral saponite at the base of the stratigraphic section in Gale crater by CheMin and the gradual transition to dioctahedral ferric smectite up section. A better understanding of the dissolution behavior of saponites would therefore help us better interpret past water-rock interactions at Gale crater. However, smectite structures and compositions are variable and complex, and very few saponite dissolution rates exist in the literature. To further understand past water-rock interactions at Gale crater, we are reporting our results to date from dissolution experiments of Fe- and Mg- saponites under a range of conditions.

Luu, N. C.↗
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↗
DOE OSTI2026

Constraining the Hydration of Clay Minerals and Abundances of Amorphous Phases in Gale Crater, Mars

Both water and organic matter are required for the development and persistence of life. Phyllosilicates (clay minerals) have high surface areas that easily sorb water and organic matter. The Curiosity rover has investigated several hundred meters of stratigraphy in Gale crater, including where clays were detected from orbit. Previous results have suggested that subsurface hydration is greatest in units with the most abundant clays, suggesting that these minerals may be hydrated. Organics have also been found throughout Gale crater. Smectites are the most common and abundant phyllosilicates in Gale crater samples and can expand and sorb water and organics in interlayer sites. The most common organic sorption processes on Earth typically involve water or hydroxyl, so hydrated phyllosilicates are good candidates for organic preservation. Using newly derived subsurface hydration results with previously published mineralogy and geochemistry, we derived modeled constraints on the abundances of hydrated amorphous phases, “excess” water, and “excess” cations. These “excess” phases are not accounted for by published crystalline phase abundances or by amorphous phases constrained here. We found correlations between smectites and both “excess” water and “excess” cation abundances, indicating that smectites in Gale crater are hydrated and that cation bridging could be a mechanism for sorption of organics. Our results also show the persistence of amorphous sulfates, opal-A, and volcanic or impact glass, which indicate low water-rock interactions. Increased abundances of sulfates and glass in stratigraphically higher samples may indicate lower water availability and environmental aridification during the time these units were being deposited.

58 GEOSCIENCES↗
DOE OSTI2023

The iron oxidation state of Ryugu samples

The Hayabusa2 mission sampled Ryugu, an asteroid that did not suffer extensive thermal metamorphism, and returned rocks to the Earth with no significant air exposure. It therefore offers a unique opportunity to study the redox state of carbonaceous Cb-type asteroids and evaluate the overall redox state of the most primitive rocks of the solar system. An analytical framework was developed to investigate the iron mineralogy and valence state in extraterrestrial material at the micron scale by combining x-ray diffraction, conventional Mössbauer (MS), and nuclear forward scattering (NFS) spectroscopies. An array of standard minerals was analyzed and cross-calibrated between MS and NFS. Then, MS and NFS spectra on three Ryugu grains were collected at the bulk and the micron scales. In Ryugu samples, iron is essentially accommodated in magnetite, clay minerals (serpentine–smectite), and sulfides. Only a single set of Mössbauer parameters was necessary to account for the entire variability observed in MS and NFS spectra, at all spatial scales investigated. These parameters therefore make up a fully consistent iron mineralogical model for the Ryugu samples. As far as MS and NFS spectroscopies are concerned, Ryugu grains are overall similar to each other and share most of their mineralogical features with CI-type chondrites. In detail however, no ferrihydrite is found in Ryugu particles even at the very sensitive scale of Mössbauer spectroscopy. The typical Fe 3+ /Fe tot of clay minerals is much lower than typical redox ratios measured in CI chondrites (Fe 3+ /Fe tot = 85%–90%). Furthermore, magnetite from Ryugu is stoichiometric with no significant maghemite component, whereas up to 12% of maghemite was previously identified in the Orgueil's so-called magnetite. These differences suggest that most CI meteorites suffered terrestrial alteration and that the preterrestrial composition of these carbon-rich samples was less oxidized than previously measured. However, it is not clear yet whether or not the parent bodies of CI chondrites were as reduced as Ryugu. Finally, the high spatial resolution of NFS allows to disentangle the redox state and the crystal chemistry of iron accommodated in serpentine and smectite. The most likely polytype of serpentine is lizardite, containing <35% of Fe 3+ , a fraction of which being tetrahedrally coordinated. Smectite is more oxidized (Fe 3+ /Fe tot > 65%) and mainly contains octahedral ferric iron. In conclusion, this finding implies that these clays formed from highly alkaline fluids and the spatial variability highlighted here may suggest a temporal evolution or a spatial variability of the nature of this fluid.

58 GEOSCIENCES↗
DOE OSTI2023

Red-green-bleached redox interfaces in the proximal Permian Cutler red beds: implications for regional fluid alteration

Siliciclastic strata of the Colorado Plateau attract attention for their striking red, green, bleached, and variegated colors that potentially record both early depositional and later diagenetic events. We investigated the proximal-most strata of the Paradox Basin, from their onlap contact with the Precambrian basement of the Uncompahgre Plateau to the younger Cutler strata exposed within 10 km of the Uncompahgre Plateau to attempt to understand the significance of the striking colors that occur here. These strata preserve a complex geology associated with buried paleorelief and sediment-related permeability variations at a major basin-uplift interface. Strata exposed within ~1.5 km of the onlap contact exhibit a pervasive drab color in contrast to the generally red colors that predominate farther from this front. In-between, strata commonly host variegated red/green/bleached intercalations. Thin-section petrography, SEM, XRD, Raman spectroscopy, Mössbauer spectroscopy, and whole-rock geochemistry of samples representing different color variations from demonstrate that water–rock interactions charged the rocks with Fe(II) that persists primarily in the phyllosilicate fraction. Color variations reflect grain-size differences that allowed the reduction of fluids from regional fault and basement/fill contacts to permeate coarser-grained Cutler sediments. Hematite and chlorite occur in both red and green sediments but are absent in the bleached sediments. Pervasive hematite in both red and green layers suggests that sediments were hematite-rich before later alteration. Chlorite and smectite are elevated in green samples and inversely correlated with biotite content. Green coloration is generally associated with 1) coarser grain sizes, 2) spatial association with basement contacts, 3) elevated smectite and/or chlorite, 4) less total Fe but greater Fe(II)/Fe(III) primarily in the phyllosilicate fraction, and 5) uranium enrichment. The bleached coloration reflects the removal of pigmentary Fe(III) oxide, while the green coloration is due to the removal of pigmentary hematite and the abundance of Fe(II)-bearing phyllosilicates. Abundant mixed-layer and swelling clays such as smectite, illite/smectite, and chlorite/smectite (including tosudite) dominate the mineralogy of the clay fraction. These results are consistent with other studies demonstrating fault-associated fluid alteration in the Paradox Basin region. However, the pervasive greening was not observed in many of these studies and appears to reflect the unique aspects of the paleovalley system and the importance of biotite alteration to Fe(II)-bearing phyllosilicates.

58 GEOSCIENCES↗
DOE OSTI2023

Interaction between clay minerals and organics in asteroid Ryugu

The Hayabusa 2 spacecraft brought back to Earth grains of the carbonaceous asteroid Ryugu. Such grains represent the pristine state of CI chondritic materials and have been preserved from exposure to Earth’s atmosphere. Here, we show evidence of the presence of organics trapped within the interlayer space of smectite layers in Ryugu grains. No such organics are found in the Orgueil CI meteorite. We put forward that the organics within the interlayer space of smectite in Orgueil CI meteorite were lost during their oxidation on Earth. Also, we propose that the presence of organics within the interlayers space of smectite might be responsible for the possible NH infrared signature observed in Ryugu particles and potentially to a few large C-type asteroids including Ceres

58 GEOSCIENCES↗