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NASA NTRSDate not supplied

Ryugu-Like Phyllosilicate Clast from A Giant Cluster IDP of Probable Cometary Origin: Evidence for Material Exchange Between Asteroidal and Cometary Regions

The presence of hydrous minerals in comets is currently an open question. They were commonly produced inside primitive meteorite parent bodies but apparently not inside the active comets that never contained liquid water. Despite examination of hundreds of particles returned from the Jupiter Family comet Wild 2 by the Stardust(SD) spacecraft, no phyllosilicates have yet been found. Near IR spectra obtained by the Rosetta spacecraft of short-period comet 67P Churyumov-Gerasimenko (67P CG) similarly did not reveal the presence of phyllosilicate minerals. IR spectral features in ejecta from comet Temple 1were interpreted as hydrated minerals but this match is controversial. Studies of a giant cluster interplanetary dust particle (IDP) have demonstrated that the IDP has a large number of chemical and physical properties consistent with its derivation from a comet including 1) its porous aggregate morphology similar to fragile aggregate particles imaged from comet 67P CG, 2) an unequilibrated mineral assemblage, 3) mineral isotopic compositions similar to like minerals in comet Wild 2, 4) uncorrelated Fe-Mn ratios of olivines that mimic those from Wild 2, 5) high presolar silicate abundance [8] and 6) Kool grains which are observed in comet Wild 2 but not in chondrites. Our examination of 70+>5 μm fragments from the IDP have shown that it is overwhelmingly composed of anhydrous silicates. We have observed, however, a 5 x 15 μm porous aggregate fragment (LT10), which contains a rare phyllosilicate clast encased in anhydrous mineral and rock fragments. We conducted detailed TEM and O isotopic analyses of this particle to constrain its origin.

D J Joswiak↗
DOE OSTI2025

Clay Reimagined: Phyllosilicates as Future Membrane Technologies

Membrane technologies have made critical advances in resource recovery, water purification, and energy systems. However, it is difficult to systematically tune properties of traditional polymer membranes, and researchers have struggled to deliver challenging, advanced separations using these platforms. In recent years, membranes based on 2D materials have drawn attention for molecular-scale separations due to their unique properties, most notably their tunable nanoscale interlayer properties. Among the diverse family of 2D materials, phyllosilicates, a broad class of naturally abundant clay minerals, offer significant advantages in cost and scalability over synthetic 2D materials, positioning them as promising candidates for advanced membrane technologies. Their inherent structural and chemical properties, strategies for tailoring selective transport pathways, and recent advancements across applications including ion separation, water treatment, and energy conversion are discussed. Finally, key challenges and opportunities are outlined to guide future research in leveraging phyllosilicate membranes for high-performance separation technologies.

energy storage and conversion↗
NASA NTRS2022

Mapping Phyllosilicates on the Asteroid Bennu Using Thermal Emission Spectra and Machine Learning Model Applications

Bennu, the target of the OSIRIS-REx mission, is an asteroid with compositions analogous to low petrologic type CI, CM, CR, and/or ungrouped carbonaceous chondrites. Asteroids like Bennu provide information about the building blocks of the early Solar System. Analysis of the mid-infrared remote sensing data informs mineral quantification. We apply a phyllosilicate specific model, developed by Breitenfeld et al. (2021) that distinguishes between Mg and Fe serpentines, to Baseball Diamond 1 (BBD1), Equatorial Station 3 (EQ3), and Touch-And-Go OSIRIS-REx Thermal Emission Spectrometer data. The average total phyllosilicate predictions are 73 (BBD1) and 72 vol% (EQ3). We observe higher Fe-cronstedtite and lower Mg-rich serpentine content in the equatorial region of Bennu than average. Mid-infrared spectral variability may be explained by sorting effects through mass movement.

Bennu↗
DOE OSTI2024

Coevolution of phyllosilicate, carbon, sulfide, and apatite in Ryugu's parent body

Abstract We analyzed an asteroid Ryugu sample returned to Earth by JAXA's Hayabusa2 mission using nanoIR, SEM, and TEM microscopy. We identified multiple distinct carbon reservoirs within the phyllosilicate matrix and demonstrate infrared spectral affinities for some of the carbon to insoluble organic matter (IOM). TEM studies of Ryugu samples have allowed us to better understand the interrelationship between the crystallographic orientations of phyllosilicates and the secondary minerals such as carbonate, sulfide, and apatite. Transport of elements provides a unifying theme for understanding these interrelationships.

Geochemistry & Geophysics↗
NASA NTRS1980

Carbonaceous chondrites. II - Carbonaceous chondrite phyllosilicates and light element geochemistry as indicators of parent body processes and surface conditions

Petrographic analyses of CM matrices characterized four phyllosilicates in Murray and Murchison meteorites and Fe- and Mg-serpentines in Nogoya. All phyllosilicates and bulk matrices show enrichment of K relative to Na when compared with bulk meteorites; the loss of Na and some Cl, and the addition of H2O, CO2, and water-soluble organics during alteration indicates a partially open system. Synthesis of soluble organic materials may have occurred in CM matrices before aqueous alteration of the precursive phases. Nogoya was 95% altered and has a bulk C content of 5.2%, higher than any meteorite; also, it has the lowest measured C-13/C-12 ratio of any carbonaceous chondrite except for Karoonda.

Bunch, T. E.↗
NASA NTRS1995

Hematite, pyroxene, and phyllosilicates on Mars: Implications from oxidized impact melt rocks from Manicouagan Crater, Quebec, Canada

Visible and near-IR refectivity, Moessbauer, and X ray diffraction data were obtained on powders of impact melt rock from the Manicouagan Impact Crater located in Quebec, Canada. The iron mineralogy is dominated by pyroxene for the least oxidized samples and by hematite for the most oxidized samples. Phyllosilicate (smectite) contents up to approximately 15 wt % were found in some heavily oxidized samples. Nanophase hematite and/or paramagnetic ferric iron is observed in all samples. No hydrous ferric oxides (e.g., goethite, lepidocrocite, and ferrihydrite) were detected, which implies the alteration occurred above 250 C. Oxidative alteration is thought to have occurred predominantly during late-stage crystallization and subsolidus cooling of the impact melt by invasion of oxidizing vapors and/or solutions while the impact melt rocks were still hot. The near-IR band minimum correlated with the extent of aleration Fe(3+)/Fe(sub tot) and ranged from approximately 1000 nm (high-Ca pyroxene) to approximately 850 nm (bulk, well-crystalline hematite) for least and most oxidized samples, respectively. Intermediate band positions (900-920 nm) are attributed to low-Ca pyroxene and/or a composite band from hematite-pyroxene assemblages. Manicouagan data are consistent with previous assignments of hematite and pyroxene to the approximately 850 and approximately 1000nm bands observed in Martian reflectivity spectra. Manicouagan data also show that possible assignments for intermediate band positions (900-920 nm) in Martian spectra are pyroxene and/or hematite-pyroxene assemblages. By analogy with impact melt sheets and in agreement with observables for Mars, oxidative alteration of Martian impact melt sheets above 250 C and subsequent erosion could produce rocks and soils with variable proportions of hematite (both bulk and nanophase), pyroxene, and phyllosilicates as iron-bearing mineralogies. If this process is dominant, these phases on Mars were formed rapidly at relativly high temperatures on a sporadic basis throughout the history of the planet. The Manicouagan samples also show that this mineralogical diversity can be accomplished at constant chemical composition, which is also indicated for Mars from the analyses of soil at the two Viking landing sites.

Morris, Richard V.↗
NASA NTRS1995

Hematite, pyroxene, and phyllosilicates on Mars: Implications from oxidized impact melt rocks from Manicouagan Crater, Quebec, Canada

Visible and near-IR reflectivity, Mossbauer, and X ray diffraction data were obtained on powders of impact melt rock from the Manicouagan Impact Crater located in Quebec, Canada. The iron mineralogy is dominated by pyroxene for the least oxidized samples and by hematite for the most oxidized samples. Phyllosilicate (smectite) contents up to 15 wt % were found in some heavily oxidized samples. Nanophase hematite and/or paramagnetic ferric iron is observed in all samples. No hydrous ferric oxides (e.g., goethite, lepidocrocite, and ferrihydrite) were detected, which implies the alteration occurred above 250 C. Oxidative alteration is thought to have occurred predominantly during late-stage crystallization and subsolidus cooling of the impact melt by invasion of oxidizing vapors and/or solutions while the impact melt rocks were still hot. The near-IR band minimum correlated with the extent of aleration (Fe(3+)/Fe(sub tot)) and ranged from approx. 1000 nm (high-Ca pyroxene) to approx. 850 nm (bulk, well-crystalline hematite) for least and most oxidized samples, respectively. Intermediate band positions (900-920 nm) are attributed to low-Ca pyroxene and/or a composite band from hematite-pyroxene assemblages. Manicouagan data are consistent with previous assignments of hematite and pyroxene to the 850 and 1000 nm bands observed in Martian reflectivity spectra. Manicouagan data also show that possible assignments for intermediate band positions (900-920 nm) in Martian spectra are pyroxene and/or hematite-pyroxene assemblages. By analogy with impact melt sheets and in agreement with observables for Mars, oxidative alteration of Martian impact melt sheets above 250 C and subsequent erosion could produce rocks and soils with variable proportions of hematite (both bulk and nanophase), pyroxene, and phyllosilicates as iron-bearing mineralogies. If this process is dominant, these phases on Mars were formed rapidly at relatively high temperatures on a sporadic basis throughout the history of the planet. The Manicouagan samples also show that this mineralogical diversity can be accomplished at constant chemical composition, which is also indicated for Mars from analyses of soil at the two Viking landing sites.

Morris, Richard V.↗
NASA NTRS2011

Phyllosilicate Deposits in Shalbatana Vallis

Shalbatana Vallis is an ancient river valley on Mars, the westernmost of the southern Chryse outflow channels. The geologic history of this area has significant implications for understanding Mars' hydrologic and climate history. The highland flood basalts are cut by large collapse depressions, multiple outflow channels, and chaotic terrain. An intravalley paleolake with a depth of over 400 m, in the 125 km diameter Orson Welles crater (Fig. 1) and the adjacent section of Shalbatana Vallis, was deduced from Mars Orbiter Laser Altimeter (MOLA) topography, evidence of shorelines and the occurrence of fan-delta deposits, including Gilbert-style deltas [1]. A number of CRISM (Compact Reconnaissance Imaging Spectrometer for Mars) images with strong phyllosilicate signatures have been identified throughout the channel and nearby highlands (Fig. 1). A majority of the signatures are concentrated in areas exposed by impact cratering. Since such minerals can form by a variety of different geological processes, such as weathering, burial diagenesis, and hydrothermal alteration [2], the nature of the phyllosilicate deposits in the Shalbatana Vallis region may provide insights into the formation processes that took place and help to place constraints on the early aqueous activity in the region.

Wintzer, Anne E.↗
NASA NTRS2011

Spitzer IRS Spectroscopy of the 10 Myr-Old EF Cha Debris Disk: Evidence for Phyllosilicate-Rich Dust in the Terrestrial Zone

We describe Spitzer IRS spectroscopic observations of the approx. 10 Myr-old star, EF Chao Compositional modeling of the spectra from 5 micron to 35 micron confirms that it is surrounded by a luminous debris disk with L(sub D)/L(sub *) approx. 10(exp -3), containing dust with temperatures between 225 K and 430 K characteristic of the terrestrial zone. The EF Cha spectrum shows evidence for many solid-state features, unlike most cold, low-luminosity debris disks but like some other 10-20 Myr-old luminous, warm debris disks (e.g. HD 113766A). The EF Cha debris disk is unusually rich in a species or combination of species whose emissivities resemble that of finely-powdered, laboratory-measured phyllosilicate species (talc, saponite, and smectite), which are likely produced by aqueous alteration of primordial anhydrous rocky materials. The dust and, by inference, the parent bodies of the debris also contain abundant amorphous silicates and metal sulfides, and possibly water ice. The dust's total olivine to pyroxene ratio of approx. 2 also provides evidence of aqueous alteration. The large mass volume of grains with sizes comparable to or below the radiation blow-out limit implies that planetesimals may be colliding at a rate high enough to yield the emitting dust but not so high as to devolatize the planetesimals via impact processing. Because phyllosilicates are produced by the interactions between anhydrous rock and warm, reactive water, EF Cha's disk is a likely signpost for water delivery to the terrestrial zone of a young planetary system.

Currie, Thayne↗
NASA NTRS2017

Unraveling the Diversity of Early Aqueous Environments and Climate on Mars Through the Phyllosilicate Record

Were Martian phyllosilicates formed on the surface or subsurface? Was early Mars warm or cold? How long was liquid water present on the surface of Mars? These are some of the many open questions about our neighboring planet. We propose that the mineralogy of the clay-bearing outcrops on Mars can help address these questions. Abundant phyllosilicates and aqueous minerals are observed nearly everywhere we can see the ancient rocks on Mars. Most bountiful among these is Fe/Mg-smectite. In this study we evaluate the nature and stratigraphy of clay outcrops observed on Mars and the presence of mixtures of other clays or other minerals with the ubiquitous Fe/Mg-smectite.

Bishop, J. L.↗
NASA NTRSDate not supplied

Phyllosilicate Formation on Early Mars Via Open-System Acid Alteration of Basaltic Glass

Smectites are widespread on Mars, but neutral/alkaline conditions favorable for smectite formation have surprisingly not led to abundant carbonates. Smectite formation on Mars could also occur in acidic environments unfavorable for carbonate formation. Acidic smectite formation has been demonstrated in batch (closed hydrologic) systems, however, the mechanisms and octahedral composition of smectite forming in acidic flow-through (open hydrologic) systems are not fully understood. Stapafell basaltic glass was hydrothermally altered (190◦C) at two flow rates corresponding to low and high water to rock ratio (W/R) and initial pH (pH_0) values of 2, 3, 4 and 6, and a batch low W/R experiment was conducted at pH_0 2. Kaolinite, montmorillonite and chlorite formed at pH_0 2 at low W/R; no phyllosilicates formed at pH_0 2 at high W/R; and lizardite formed at pH_0 ≥3 at both W/R ratios. Lizardite, kaolinite, and montmorillonite in these experiments formed by precipitation from solution and chlorite likely formed through alteration of montmorillonite and/or basalt. Saponite formed at pH_0 2 in batch conditions by alteration of basaltic glass. Comparison of experimental data with martian phyllosilicate assemblages indicated that smectite formation on Mars likely occurred under water-limited conditions. Al-rich smectite could form in open-system low W/R subsurface environments under a narrow range of pH (pH <3) while saponite could form in closed low W/R systems under acidic to alkaline conditions. Combined open and closed hydrological regimes could be responsible for development of clay mineral stratigraphies observed on Mars. The acidic conditions required for formation of Al-rich smectite were unfavorable for carbonate precipitation, but carbonate precipitation could occur together with Fe/Mg-smectite in closed systems at pH >4. The lack of carbonates occurring together with Fe/Mg-smectite could be cause by low pCO2 in subsurface closed environments and/or by overall lack of carbonate precipitation despite significant oversaturation.

S J Ralston↗
NASA NTRS2023

Phyllosilicate Decomposition on Bennu Due to Prolonged Surface Exposure

The Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer (OSIRIS-REx) mission to carbonaceous asteroid (101955) Bennu performed detailed mapping with a suite of instruments to characterize the composition and geology of its surface. Here we use data from the OSIRIS-REx Thermal Emission Spectrometer (OTES) instrument to investigate the relationship of OTES-derived spectral indices to other derived data products from OTES, the OSIRIS-REx Camera Suite (OCAMS), and the OSIRIS-REx Visible and InfraRed Spectrometer (OVIRS) at global and local scales. We quantitatively confirm that high values of the OTES silicate stretching slope (from ∼10 to ∼12 μm) in midday spectra that are indicative of thin and/or patchy dust cover are strongly associated with low thermal inertia (high porosity), low albedo boulders on Bennu. These high porosity boulders have brecciated textures with embedded clasts that likely originated on Bennu's parent body or during its disruption. The high porosity of these boulders is a key factor in the local production of the dust or its entrapment, as some large, brecciated boulders with a lower porosity have little evidence of dust. A second OTES spectral parameter, the silicate bending band depth near 22.7 μm applied to early evening spectra, is not correlated to thermal inertia, but is weakly to strongly correlated to albedo, OVIRS-derived 1.05 μm and 2.74 μm band depths, OVIRS-derived hydrogen abundance, and modeled nanophase troilite abundance. In several regions on Bennu there is a strong spatial relationship between these parameters, whereby areas with shallower silicate bending bands also have shallower 1.05 μm and 2.74 μm bands and lower albedo with higher nanophase troilite abundances. These correlations, combined with analysis of the silicate bending band in laboratory experiments of space weathered and mildly heated carbonaceous chondrites, suggests that decreased silicate bending band depths signify decomposition of phyllosilicates, likely Fe-bearing, due to space weathering or mild heating (<600 °C) via solar radiation during Bennu's time in near-Earth space. There is a strong association of larger silicate bending band depths in areas dominated by small rocks and unresolved material and in areas with small (≤ 25 m) craters identified as the spectrally reddest on Bennu, suggesting that this material has been more recently exposed due to impact and/or mass wasting processes. The shallowest silicate bending depths are associated with larger rocks and boulders that appear to have the longest surface exposure history, although there is band depth variation among them suggesting either initial composition variation that resulted in different responses to space weathering or heating, or varied exposure history of individual boulders themselves. We predict that any grains returned from Bennu with a significant surface exposure history will be characterized by shallower 22.7 μm, 1.05 μm and 2.7 μm band depths and increased sulfide (troilite) abundance, as well as textural and chemical evidence for phyllosilicate dehydration.

Asteroids, surfaces↗
DOE OSTI2023

Evaluation of adsorption and mechanical strength of 13X zeolite mixtures with phyllosilicate binders using molecular dynamics simulation and positron annihilation spectroscopy

There is growing interest in developing zeolites with novel internal structures that have optimal adsorptive capacity and high mechanical strength, while offering advantages, such as being light weight. We integrate computational and experimental methods to explore the effect of binder/zeolite types, and weight percentages on the mechanical strength of 13X zeolite and adsorption capacities of N 2 , H 2 O, and CO 2 for additive manufacturing (AM) applications with the goal of maximizing both adsorption and strength. Zeolite 13X mixtures and phyllosilicate binders (either bentonite or kaolin) are combined using molecular dynamics (MD) simulations to create structures with various binder/zeolite weight percentages. Further, adsorption capabilities and mechanical strength are assessed using the grand canonical Monte Carlo (GCMC) and ReaxFF modules, respectively. Our modeling shows that an optimized zeolite/binder ratio for N 2 adsorption is around 15 wt% for kaolin and roughly 10 wt% for bentonite. The resulting parameters can be applied to facilitate macro-scale computational fluid dynamics (CFD) and finite element method (FEM) simulations of an AM zeolite structure. We also performed Positron Annihilation Lifetime Spectroscopy (PALS) measurements on zeolite samples to explore the effect of changes in the internal volume. The results show an inverse relationship between the free volume and the solid loading and adding a binder changes the morphology of the zeolite-binder compound and decreases open-volume area significantly.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Iron XANES measurements of carbonates and phyllosilicates in CM chondrites: A record of redox conditions during aqueous alteration

Multiple generations of calcite and dolomite precipitated in CM chondrites during ice melting events that led to episodes of liquid water. Models and laboratory analysis have suggested a long-term transition from oxidizing to reducing conditions during aqueous alteration on the CM parent body. We found that synchrotron X-ray absorption near edge spectroscopy (XANES) can detect relative differences in the oxidation state of trace iron within these carbonates. In CM chondrites, previous work interpreted Mn abundance in calcite as an indicator of relatively early or late formation, and dolomite is understood to form relatively late. In the CM1 chondrite Meteorite Hills 01070, XANES maps reveal that Mn-poor calcite contains more oxidized iron relative to Mn-rich calcite. While these measurements of carbonates support increasing iron reduction with progressive aqueous alteration in MET 01070, comparison among different CM chondrites suggests a complex picture of redox evolution. In addition to carbonates, we performed XANES measurements of the phyllosilicate-rich matrix of Allan Hills 83,100. Pre-edge centroid analysis indicates that this CM1/2 has an oxidation state similar to typical CM2 chondrites. While additional measurements are warranted to confirm the full span of redox trends in CM carbonates, our data do not support a correlation between redox state and petrologic type.

Bailey, Elizabeth [Univ. of California, Santa Cruz↗
DOE OSTI2021

AFM Slip Length Measurements for Water at Selected Phyllosilicate Surfaces

Most reported slip length measurements have been made at the surfaces of synthetic materials and modified synthetic materials. In contrast, few slip length measurements at the surface of unmodified natural mineral surfaces have been reported. In this regard, flow at the silica face surfaces of the phyllosilicate minerals, talc and mica, was considered. A slip boundary condition was expected at the nonpolar hydrophobic silica surface of talc leading to enhanced flow, and a no-slip boundary condition was expected at the hydrophilic silica surface of mica. Atomic force microscopy (AFM) slip length measurements were made at the talc and mica surfaces. The slip length results for the hydrophobic silica surface of talc were contrasted to the results for the hydrophilic silica surface of mica (no-slip flow). The results are discussed based on molecular dynamics simulations (MDS), as reported in the literature, and AFM images of surface nanobubbles. For nonpolar hydrophobic surfaces (such as talc), it is doubtful that the MDS interfacial water structure and the water exclusion zone (3.2 Å) account for the AFM slip flow with slip lengths as great as 95 nm. Rather, a better explanation for the AFM slip flow condition is based on reduced interfacial viscosity due to the presence of dissolved gas and the accommodation of pancake nanobubbles at the talc surface having a height dimension of magnitude similar to the slip length.

42 ENGINEERING↗
NASA NTRS1977

Correlation between nickel and sulfur abundances in Orgueil phyllosilicates

Sympathetic variations in nickel and sulfur abundances, on a scale of micrometers, in Orgueil phyllosilicates apparently reproduce similar correlations among matrices of different carbonaceous chondrites. In Orgueil this effect probably results from aqueous alteration of a Ni-Si-bearing phase on the parent body.

Kerridge, J. F.↗