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At least 163 records · Page 9

Dissolution Rates of Allophane with Variable Fe Contents: Implications for Aqueous Alteration and the Preservation of X-ray Amorphous Materials on Mars

Recent measurements from Mars document X-ray amorphous/nano-crystalline materials in multiple locations across the planet. However, despite their prevalence, little is known about these materials or what their presence implies for the history of Mars. The X-ray amorphous component of the martian soil in Gale crater has an X-ray diffraction pattern that can be partially fit with allophane (approximately Al2O3•(SiO2)1.3-2•(H2O)2.5-3), and the low-temperature water release data are consistent with allophane. The chemical data from Gale crater suggest that other silicate materials similar to allophane, such as Fe-substituted allophane (approximately (Fe2O3)0.01-0.5(Al2O3)0.5-0.99•(SiO2)2•3H2O), may also be present. In order to investigate the properties of these potential poorly crystalline components of the martian soil, Fe-free allophane (Fe:Al = 0), Fe-poor allophane (Fe:Al = 1:99), and Fe-rich allophane (Fe:Al = 1:1) were synthesized and then characterized using electron microscopy and Mars-relevant techniques, including infrared spectroscopy, X-ray diffraction, and evolved gas analysis. Dissolution experiments were performed at acidic (initial pH values pH0 = 3.01, pH0 = 5.04), near-neutral (pH0 = 6.99), and alkaline (pH0 = 10.4) conditions in order to determine dissolution kinetics and alteration phases for these poorly crystalline materials. Dissolution rates (rdiss), based on the rate of Si release into solution, show that these poorly crystalline materials dissolve approximately an order of magnitude faster than crystalline phases with similar compositions at all pH conditions. For Fe-free allophane, logrdiss = -10.65 – 0.15 × pH; for Fe-poor allophane, logrdiss = -10.35 – 0.22 × pH; and for Fe-rich allophane, logrdiss = -11.46 – 0.042 × pH at 25°C, where rdiss has the units of mol m-2 s-1. The formation of incipient phyllosilicate-like phases was detected in Fe-free and Fe-rich allophane reacted in aqueous solutions with pH0 = 10.4 (steady-state pH ≈ 8). Mars-analog instrument analyses demonstrate that Fe-free allophane, Fe-poor allophane, and Fe-rich allophane are appropriate analogs for silicate phases in the martian amorphous soil component. Therefore, similar materials on Mars must have had limited interaction with liquid water since their formation. Combined with chemical changes expected from weathering, such as phyllosilicate formation, the rapid alteration of these poorly crystalline materials may be a useful tool for evaluating the extent of aqueous alteration in returned samples of martian soils.

S J Ralston↗

Spectral Effects of Varying Texture and Composition in Two-component “Mudpie” Simulations: Insights for Asteroid (101955) Bennu

Data returned by the OSIRIS-REx (Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer) spacecraft have shown that asteroid (101955) Bennu has a globally low-albedo surface covered in boulders with diverse texture, color, and albedo properties, and an aqueously altered composition dominated by phyllosilicates. To test whether Bennu’s color and albedo diversity could be caused by texture and/or composition variations, we performed a laboratory-based study using simple two-component mixtures (called “mudpies”) of the phyllosilicate saponite and carbon-rich opaques. Each mudpie is prepared in four different textures: fine powder, coarse particles, sanded slab, and textured rock. We find that a sanded slab made from 90% saponite and 10% lampblack is a good analog for Bennu, and the color and albedo changes due to texture variations are substantial. At 550 nm, texture changes alone can create up to 36% brightness contrast, and in color measured as a 473 nm/847 nm ratio, texture changes can provide up to 18% color contrast. In comparison, Bennu shows approximately 25% albedo and <1% color contrasts from boulder type to boulder type. These findings suggest that if texture contributes to color on Bennu, the texture variations are typically more subtle than what we simulated in the laboratory. According to our study, the color and albedo properties of different boulder types on Bennu are consistent with different concentrations of carbon-rich opaques (and possibly consistent with variations in carbonate concentration). The variations within each boulder group are consistent with textural differences.

Antara Sen↗

Oxygen isotopic mapping of a clast in fragment C0002 from asteroid Ryugu

The samples of Ryugu returned by the Hayabusa2 spacecraft have mineralogy similar to CI chondrites and are dominated by secondary phases(e.g., phyllosilicates, carbonates, magnetite, sulfides) from extensive parent body aqueous alteration. Anhydrous minerals such as olivine, pyroxene, and spinel are rare and exist in phyllosilicate-rich clasts [2-4]. Oxygen isotopic studies of these minerals have shown a bimodal distribution with both 16O-rich and 16O-poor grains. In this study, we conducted NanoSIMS isotopic mapping of a clast found in a fragment of a C0002 grain from Chamber C, which may have derived from the asteroid sub-surface, to characterize small primary minerals

A N Nguyen↗

Unraveling Solar Wind Space Weathering of Carbon-Rich Asterods: Low-Flux VS. High-Flux Ion Irradiation of Murchison

Introduction: Space weathering processesalter the microstructural, compositional, and optical properties of airless planetary surfaces.Solar wind space weatheringforms ion-damaged rims within the outermost ~100 nm of regolith grains through atomic-displacements and implantation of energetic H+and He+ions[1]. Transmission electron microscope(TEM)studies of space weathered Itokawa and lunar olivine particles reveal predominantly nanocrystalline solar wind-damaged rims with only minor regions of amorphization[2-5]. This finding differs from laboratoryion irradiation experiments in which samples become amorphous at fluences 2-3 orders of magnitude lower than the independentlyconstrained fluences for still-crystalline natural samples [6-7].Ion flux is generally considered to have a secondaryeffectcompared to fluence in these irradiation experiments. However, solar wind irradiation of natural samples occurs at a flux that is ~4-5 orders of magnitude lower than whatisused inlaboratory simulations (e.g., [6,8-9]). Constraining how the very low ion flux of solar wind influences the microstructural, chemical, and spectral alteration of silicate minerals will improve our understanding of solar wind space weathering and aid in the analysis of returned samples from the Hayabusa2 and OSIRIS-REx missions. Here we report results from low-and high-flux ion irradiation experiments on the Murchison (CM2)meteoritewithcomparable total fluences. Methods: We performed low-flux and high-flux He+(4 keV) and H+(1 keV) irradiation experiments on separate, dry-cut Murchison slabs. Low-flux He+irradiation reached a total fluence of 2.1 x 1016ions/cm2(~400 years of exposure at Bennu) using a flux of 3.6 x 1011ions/cm2/s; low-flux H+irradiation reached a total fluence of 3.9 x 1016ions/cm2(~30 years) using a flux of 6.6 x 1011ions/cm2/s. High-flux He+irradiation reached a total fluence of 2.0 x 1016ions/cm2(~400 years)using a flux of 9.1 x 1012ions/cm2/s; high-flux H+irradiation reached a total fluence of 5.8 x 1016ions/cm2(~50 years)using flux of 8.4 x 1012ions/cm2/s. By irradiating to similar total fluences in both the low-flux and high-flux experiments, we can better isolate and evaluatethe effects of ion flux. Differences between unirradiatedand irradiated surfaces are determined using threeanalytical techniques:(1) in situX-ray photoelectron spectroscopy(XPS) reveals changes in surface chemistry,(2) visible to near-infrared spectroscopy (VNIR; 0.35-2.5 μm) highlights changes in spectraltrends, such as albedo and slope, and (3) TEM and energy-dispersive X-ray spectroscopy (EDS) identifieschanges in nanoscale structure and elemental composition within olivine and matrix electron-transparent thin sections prepared using focused ion beam scanning electron microscopy (FIB-SEM). Results and Discussion: XPS analyses of the low-fluxand high-fluxHe+-and H+-irradiated samples showa minorreduction in surface carbon contentand chemicalreduction ofFe3+to Fe2+. The latter result is consistent with the higher Fe2+/Fe3+ratios observed in phyllosilicate-rich space weathered rims of Ryugu grains [10].VNIR analyses suggest that the low-flux H+-irradiated spectrum has a slightly bluer slope (over 0.65-2.5 μm) compared to the unirradiated VNIR spectrum from [9] while the low-flux He+-irradiated spectral slope is comparable to the unirradiated surface. Both the high-flux He+-and H+-irradiated VNIR spectra exhibitslightlyhigheralbedos at shorter wavelengths relativeto their unirradiated counterparts, with He+irradiation yielding a greater change. Thus far, the low-flux He+-irradiated matrix and olivine FIBsections as well as the low-flux H+-irradiated olivine FIBsection have been examined with TEM. The surfaces of all three samplesshowless vesiculation than high-flux/high-fluenceirradiated matrix and olivine samples from [9]. The depth of phyllosilicate amorphization in thelow-fluxHe+-irradiated matrix FIBsection varieslaterally, with crystalline domains occurring as shallow as ~25 nm in some regions. Thelow-flux He+-irradiated olivine FIBsection has acontinuous,~40-90 nm thick ion-affected layer with polycrystalline and amorphous microstructures. The low-flux H+-irradiated olivine sampleexhibits a distinct, ~10-40 nm ion-affected layer whose uppermost ~20 nmin thicker regions is predominantly amorphous.Continuing to compare results from this work to those from [9] will provide a comprehensive understanding of how ion flux impacts the microstructural, chemical, and optical modification of various mineral phases and, in turn,help identify space weathering features from parent body alteration in Hayabusa2 and OSIRIS-REx returned samples.

D L Laczniak↗

Mars Science Laboratory Mastcam Multispectral Investigation of Drill Targets From the Beginning of the Clay Sulfate Transition to Marker Band Valley

In March, 2021 the Mars Science Laboratory Curiosity rover officially started exploring the Clay Sulfate Transition (CST). This area of Mt. Sharp has been interpreted to have hydrated Mg-sulfate spectral signatures in CRISM orbital data, and it no longer has the strong phyllosilicate spectral signature as the previous Glen Torridon region. Recently, the Curiosity rover has also encountered the marker band that was also identified in orbital data [1,3]. This shift from phyllosilicates to hydrated Mg-sulfates suggests a major change in the environmental conditions during which these rocks were deposited. This abstract focuses on changes seen in the Mastcam multispectral data between the CST drill targets.

S R Jacob↗

Pillared Laminar Vermiculite Membranes with Tunable Monovalent and Multivalent Ion Selectivity

Effective membrane separation of Li + from Na + and Mg 2+ is crucial for lithium extraction from water yet challenging for conventional polymeric membranes. Two dimensional (2D) membranes with ordered laminar structures and tunable physicochemical properties offer distinctive ion-sieving capabilities promising for lithium extraction. Recently, phyllosilicates are introduced as abundant and cost-effective source materials for such membranes. However, their water instability and low inherent ion transport selectivity hinder practical applications. Herein, a new class of laminar membranes with excellent stability and tunable ion sieving is reported by incorporating inorganic alumina pillars into vermiculite interlayers. Crosslinking vermiculite flakes with alumina pillars significantly strengthens interlamellar interactions, resulting in robust water stability. Doping of Na + before the pillaring process reverses the membrane's surface charge, substantially boosting Li + separation from multivalent cations via electrostatic interactions. Lithium extraction is often complicated by the presence of co-existing monovalent cations (e.g., Na + ) at higher concentrations. Here, by introducing excess Na + into the membrane after the pillaring process, the separation of Li + from monovalent cations is enhanced through steric effects. This work realizes both monovalent/multivalent and monovalent/monovalent selective ion sieving with the same membrane platform. A separation mechanism is proposed based on Donnan exclusion and size exclusion, providing new insights for membrane design for resource recovery applications.

2D materials↗

Triple oxygen and hydrogen stable isotope composition of water in Murchison carbonaceous chondrite accessed by thermogravimetry-enabled laser spectroscopy

For this work, we have developed the capability to measure 17 O/ 16 O in H 2 O and OH - of hydrous minerals by a technique using thermogravimetric analysis coupled with isotope ratio infrared spectroscopy (TGA-IRIS) on a suite of liquid water standards, terrestrial mineral standards, multi-mineral synthetic mixtures of terrestrial samples, and Murchison carbonaceous chondrite. This 17 O/ 16 O analytical capability is combined with the previously developed TGA-IRIS capability of 18 O/ 16 O, which enables us to calculate Δ `17 O values. Additionally, we have made 2 H/ 1 H measurements by TGA-IRIS on the suite of materials. Analyses of 328 standard water samples sealed into silver tubes (0.25 μL, 174 VSMOW and 154 GISP) analyzed over the course of three years yielded δ 18 O values by TGA-IRIS with precision of ±0.30 ‰, δ 17 O of ±0.24 ‰, Δ `17 O of ±0.126 ‰, and δ 2 H ± 7.5 ‰ (± 1 Std. Dev.). TGA-IRIS analyses of a suite of hydrous minerals (oxy-hydroxide, mica, serpentines, sulfide, phyllosillicates) yields similar precision. TGA-IRIS analyses of the CM2 carbonaceous chondrite Murchison resulted in δ 18 O, δ 17 O, Δ `17 O, and δ 2 H values of the H 2 O and/or OH - from its hydrous minerals. Δ `17 O values of Murchison H 2 O range from 1.034 ‰ at 350 °C, to -0.368 ‰ at 650 °C, to -1.75 ‰ at 850 °C. TGA-IRIS can generate Δ `17 O values of H 2 O and/or OH - in hydrous materials that are well within the precision needed for the analysis of meteoritic samples, as well as samples returned from asteroids, such as Ryugu and Bennu.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Accumulation of Soil Microbial Necromass Controlled by Microbe–Mineral Interactions

Soil organic matter (SOM) is a key reservoir for global carbon (C), supporting soil fertility and influencing greenhouse gas emissions. Microbial residues, composed of dead cells and cellular fragments, are major contributors to SOM formation. Yet, mechanisms by which minerals enhance the accumulation of microbial residues remain poorly understood. Here, we used 13 C-labeled glucose in a year-long incubation to trace microbial residue in sandy and silty soils. Across both soils, approximately 89% of retained microbial 13 C was recovered in the fine (<53 μm) mineral-associated organic matter (MAOM) pool. Within this pool, the light MAOM fraction, enriched in poorly crystalline Fe minerals, held 4.3 times more 13 C than the heavy, phyllosilicate-dominated MAOM fraction, despite accounting for only 17.2% of the total MAOM mass and 12.3% of the total soil mass. Along with 13 C enrichment, the light MAOM fraction showed greater abundance of N-containing groups, e.g., (amides and amino groups), indicative of microbial-derived compounds like proteins and amino sugars. Fe oxides in light MAOM from both soils were spatially dispersed. Microbial residue accumulation was greater in finer-textured silty soil. These findings demonstrate that mineral composition and texture jointly regulate microbial necromass accrual, highlighting light MAOM as a key pool for enhancing soil C storage.

13C isotope labeling↗

Variations of organic functional chemistry in carbonaceous matter from the asteroid 162173 Ryugu

Abstract Primordial carbon delivered to the early earth by asteroids and meteorites provided a diverse source of extraterrestrial organics from pre-existing simple organic compounds, complex solar-irradiated macromolecules, and macromolecules from extended hydrothermal processing. Surface regolith collected by the Hayabusa2 spacecraft from the carbon-rich asteroid 162173 Ryugu present a unique opportunity to untangle the sources and processing history of carbonaceous matter. Here we show carbonaceous grains in Ryugu can be classified into three main populations defined by spectral shape: Highly aromatic (HA), Alkyl-Aromatic (AA), and IOM-like (IL). These carbon populations may be related to primordial chemistry, since C and N isotopic compositions vary between the three groups. Diffuse carbon is occasionally dominated by molecular carbonate preferentially associated with coarse-grained phyllosilicate minerals. Compared to related carbonaceous meteorites, the greater diversity of organic functional chemistry in Ryugu indicate the pristine condition of these asteroid samples.

Science & Technology - Other Topics↗

Two-dimensional talc as a natural abundant ultra-broadband hyperbolic material

Here, we demonstrate that two-dimensional talc, a naturally abundant phyllosilicate mineral, supports hyperbolic phonon-polaritons (HPhPs) across the mid- and far-infrared wavelengths. Using scattering scanning near-field optical microscopy (s-SNOM) and synchrotron infrared nano-spectroscopy (SINS), we reveal tunable HPhP modes in talc flakes with long lifetimes, high confinement, and quality factors of up to 5. We further observe Fabry–Pérot cavity modes in tapered flakes, confirmed by simulations and analytical modeling. Compared to synthetic crystals, talc offers an ultra-broadband, low-cost, and sustainable platform for infrared nanophotonics and optoelectronics.

36 MATERIALS SCIENCE↗

Mineral-associated organic matter is heterogeneous and structured by hydrophobic, charged, and polar interactions

The formation of mineral-associated organic matter (MAOM) is a key phenomenon that may explain the slow turnover rates of carbon in soil organic matter (SOM). Despite this, important details pertaining to the structure and dynamics of MAOM remain unknown. In the present study, we use replica-exchange molecular dynamics simulations to gain insight into the structure of MAOM on the surface of prototypical phyllosilicate clay and Fe-oxide minerals, montmorillonite and goethite, fine-grained minerals that strongly impact soil carbon dynamics in temperate and tropical regions, respectively. We examine the impact of aqueous chemistry through the presence of either Na + or Ca 2 + charge balancing counterions. Our results are consistent with the hypothesized multilayer sorption (“onion-skin”) model of MAOM and help to explain previous observations regarding the patchy distribution of SOM on mineral surfaces. In particular, the SOM coatings are partial and laterally heterogeneous, and water retains extensive access to mineral surfaces even when significant SOM sorption occurs. Low molecular weight neutral SOM molecules ( < 200 Da) infrequently interact with the mineral surfaces nor their sorbed organic matter coatings and are increasingly labile with decreasing molecular weight. This observation is inconsistent with a central feature of the predominant soil continuum model of SOM and suggests that further iterations of the conceptual model may be required.

54 ENVIRONMENTAL SCIENCES↗

Investigation of mechanochemical interactions of hydrogen with earth materials in a subsurface gas storage

The goal of this project is to investigate the molecular interactions of H 2 with earth materials (EMs) that may potentially affect economics and safety of H 2 geological storage (HGS). We investigated (1) the H 2 intercalation into interlayers of phyllosilicates, (2) the competitive adsorption of H 2 /CH 4 onto porous materials, and (3) solubility of H 2 in interfacial and confined hydrocarbons. Our results indicate that (i) H 2 intercalation into hydrated interlayers is thermodynamically unfavorable and H 2 solubility in hydrated clay interlayers is in the same order of magnitude as that in bulk water, (ii) CH 4 outcompetes H 2 in adsorption onto kerogen, due to stronger CH 4 -kerogen interactions than H 2 -kerogen interactions, (iii) H 2 tends to dissolve more in oil than in water, and the introduction of CO 2 as a cushion gas reduces H 2 partitioning near the kaolinite surfaces. The outcomes provide foundational knowledge for preparing the USA for future storage site selection and storage system design, supporting DOE missions in clean and secured energy.

08 HYDROGEN↗

Cosmic abundance of iron and nature of primitive material in meteorites.

Comparison of solar abundance data with bulk analyses of type-I carbonaceous meteorites and microprobe analyses of type-I phyllosilicates. The comparison seems to lend support to Kerridge's (1971) hypothesis that the apparently primitive chemistry of such meteorites may be the result of a major component dominating the analysis and that this component may be unaltered solar system condensate.

Kerridge, J.↗

Surface properties of the Orgueil meteorite - Implications for the early history of solar system volatiles

The Kr and H2O adsorption properties of Orgueil were studied. Dehydration by stepwise calcination produced a tenfold change in its B.E.T. surface area, which increased to 120 and then fell to 40 square meters per gram. Water exchangeability was measured by water regain from lab air between calcination cycles. Dehydration at room temperature showed that Orgueil contained 6 per cent by weight of water adsorbed on free surfaces. These results are consistent with an identification of Orgueil as montmorillonite, although chemical data conflict with this. High D/H ratios in CI carbonaceous chondrites may result from D enrichment in OH- groups during equilibration of dispersed phyllosilicate dust with preplanetary nebula gas at temperatures much less than 0 C.

Fanale, F. P.↗

Infrared spectra of carbonaceous chondrites and the composition of interstellar grains

Infrared spectra (7 to 40 microns) of the Cold Bokkeveld, Murray, and Orgueil carbonaceous chondrites are compared with phyllosilicate-mineral and interstellar-grain spectra. Similarities in the position and shape of the silicate feature near 9.8 microns suggest that similar silicate minerals are present in primitive meteorites and the interstellar dust.

Zaikowski, A.↗

Mineralogic and petrologic study of the low-temperature minerals in carbonaceous chondrites

Samples and petrographic thin sections of the Orgueil, Ivuna, and Alais chondrites were examined by optical, X-ray, and SEM techniques. Mineral species identified as primary vein constituents were epsomite, gypsum, and a calcium-magnesium carbonate. Relative abundances and textural relationships have suggested that fracture mineralization was a multi stage process, with individual mineralizations closely associated with impact brecciation events. Mass balance considerations of carbonaceous chondrite matrix support the prevailing view that the source of the fracture filling minerals was local. By inference they also suggest that the phyllosilicate matrix has been chemically altered and that there are probably very few primitive mineral phases in the primitive Cl chondrites.

Wood, J. A.↗

Formation chronology for C2 meteorites

The times at which phyllosilicate matrix and euhedral olivines became associated have been determined for five C2 meteorites. The ages, calculated from fission track densities on crystal surfaces, are based on an initial Pu-244/U-238 ratio in the matrix material of 0.0154 at 4.6 b.y., and range from 4.22 b.y. for Nogoya to 4.42 b.y. for Murray. Unless the initial Pu-244/U-238 ratio was less than 0.004, the meteorites cannot have existed in their present form for 4.6 billion years. The measured ages place limits on the time when pre-compaction effects such as micrometeorite craters and solar flare tracks were produced, and they may approximately date the formation of the olivine crystals themselves.

Macdougall, J. D.↗

Textural evidence bearing on the origin of isolated olivine crystals in C2 carbonaceous chondrites

In some cases the mechanical competence of chondrules in carbonaceous chondrites has been reduced by alteration of their mesostasis glass to friable phyllosilicate, providing a mechanism by which euhedral olivines can be separated from chondrules. Morphological features of isolate olivine grains found in carbonaceous chondrites are similar to those of olivine phenocrysts in chondrules. These observations suggest that the isolated olivine grains formed in chondrules, by crystallization from a liquid, rather than by condensation from a vapor.

Richardson, S. M.↗