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At least 55 records · Page 3

Ground Truthing Orbital Clay Mineral Observations with the APXS Onboard Mars Exploration Rover Opportunity

NASA's Mars Exploration Rover Opportunity has been exploring approximately 22 km diameter Endeavour crater since 2011. Its rim segments predate the Hesperian-age Burns formation and expose Noachian-age material, which is associated with orbital Fe3+-Mg-rich clay mineral observations [1,2]. Moving to an orders of magnitude smaller instrumental field of view on the ground, the clay minerals were challenging to pinpoint on the basis of geochemical data because they appear to be the result of near-isochemical weathering of the local bedrock [3,4]. However, the APXS revealed a more complex mineral story as fracture fills and so-called red zones appear to contain more Al-rich clay minerals [5,6], which had not been observed from orbit. These observations are important to constrain clay mineral formation processes. More detail will be added as Opportunity is heading into her 10th extended mission, during which she will investigate Noachian bedrock that predates Endeavour crater, study sedimentary rocks inside Endeavour crater, and explore a fluid-carved gully. ESA's ExoMars rover will land on Noachian-age Oxia Planum where abundant Fe3+-Mg-rich clay minerals have been observed from orbit, but the story will undoubtedly become more complex once seen from the ground.

Schroeder, C.↗

Glen Torridon Mineralogy and the Sedimentary History of the Clay Mineral Bearing Unit

Clay minerals are common in ancient terrains on Mars and their presence at the surface alludes to aqueous processes in the Noachian to Early Hesperian (>3.5 Ga). Gale crater was selected as Curiosity’s landing site largely because of the identification of clay mineral rich strata from orbit. On Earth, the types of clay minerals (i.e., smectites) identified in Gale crater are typically juvenile weathering products that ultimately record the interaction between primary igneous minerals with the hydrosphere, atmosphere, and biosphere. Trioctahedral and dioctahedral smectite were identified by Curiosity in units stratigraphically below the Clay Mineral-Bearing Unit (CBU) identified from orbit. Compositional and sedimentological data suggest the smectite formed via authigenesis in a lake environment and may have been altered during early diagenesis. The CBU is stratigraphically equivalent to a hematite-rich unit to the north and stratigraphically underlies sulfate-rich units to the south, suggesting a dynamic environment and evolving history of water in the ancient Gale crater lake. Targeting these clay mineral rich areas on Mars with rover missions provides an opportunity to explore the aqueous and sedimentary history of the planet.

Thorpe, M. T.↗

Competitive Sorption of H 2 O and CO 2 in Clay Mineral Interlayers

The first-reported competitive CO 2 –H 2 O sorption isotherms on a naturally occurring expandable clay mineral (saponite) exchanged with Na, K, and Cs at near ambient CO 2 concentrations (1% CO 2 ) are reported by combining ATR-FTIR spectroscopy with gravimetric sorption methods. Little CO 2 sorption was observed at high relative humidity (RH) but increased significantly at low RH. Unlike prior work where CO 2 sorption was reported on samples that were previously subjected to heating and/or evacuation treatment to remove sorbed H 2 O, this study manipulated CO 2 sorption by controlling RH. CO 2 sorption increased in the order Cs- > K- > Na-exchanged saponite and was anticorrelated with the Gibbs energy of hydration of the exchangeable cation. As expected, H 2 O sorption followed the opposite trend, with increased H 2 O sorption occurring in the order Na > K > Cs. The amount of CO 2 sorbed using 1 atm CO 2 (p/p o = 1.0) ranged from 50 to 30 mg CO 2 /g clay and from 1.25 to 0.8 mg CO2 /g clay for 1% CO 2 (p/p o = 0.01) in N 2 . The sensitivity of the ATR-FTIR measurements is demonstrated by detecting the CO 2 stretch of adsorbed CO 2 from air containing 500 ppmv CO 2 . The spectral features of sorbed CO 2 were minimally affected by the nature of the exchangeable cation or variations in H 2 O content. However, the position of the HOH bending band shifted significantly from 1638 to 1610 cm –1 as H 2 O content decreased, reflecting changes in intermolecular hydrogen bonding between H 2 O molecules in the saponite interlayer. The shift in position of the HOH bending band to lower energy was coincident with increased CO 2 sorption. CO 2 sorption in clay mineral interlayers is consistent with sorption on weakly hydrated partially hydrophobic sites found on low charge density smectites and is enhanced by lower RH and by the presence of weakly hydrated exchangeable cations like Cs + or K + . In conclusion, the greatest CO 2 sorption occurs on Cs-saponite because this is the least hydrated cation of the three used in the study and indicates that CO2 sorption occurs on the neutral portion of the siloxane surface.

Johnston, Cliff T. [Purdue Univ., West Lafayette, ↗

Control Mechanisms for Self‐Sealing in Activated Clay‐Rich Faults Through Controlled Hydraulic Injection Experiment

Abstract In a high‐pressure injection fault activation experiment conducted at the Mont Terri underground research laboratory in Switzerland, the transmissivity of the Opalinus Clay fault significantly increased due to opening and shearing. The fluid injection, spanning a few hours, generated a 10 m radius fault activation patch. Subsequent pressure pulse tests conducted bi‐weekly for a year revealed the gradual return of fault transmissivity to its initial state. The study utilized fluid pressure decay analysis, optical fiber monitoring, continuous active source seismic measurements and borehole displacement sensors for measuring fault displacements. The fault zone exhibited a dilation of approximately 1.4 mm, associated with both normal and tangential movements during activation, resulting in a sudden transmissivity increase from 1 × 10 −12 to 3.2 × 10 −7 m 2 /s. Early post‐activation, transient compaction and the subsequent slow compaction were observed, transitioning to an extension regime. The pressure pulse tests demonstrated a rapid transmissivity drop by more than two orders of magnitude within the first 10 days, followed by a gradual and less pronounced decrease. Plastic shear and compaction dominated the transmissivity evolution until 70 days after injection ended, followed by a period where additional factors, such as clay mineral swelling, influenced the behavior. Extrapolation suggested a sealing process taking at least 50 years after the initial activation. Plain Language Summary A field‐scale fault activation experiment offers valuable insights into the elasto‐plastic processes governing the sealing of shale faults. The experiment reveals a rapid increase in the fault's transmissivity by approximately five orders of magnitude during activation. Subsequent observations show a gradual transmissivity decrease by about three orders of magnitude post‐activation, with slow long‐term plastic shear and compaction of the fault competing against secondary processes, notably clay mineral swelling. All conceptual models employed to interpret these field data converge on the estimation that the fault's return to its initial low transmissivity state would require a minimum of 50 years. Key Points High‐pressure injection fault activation experiment at the Mont Terri underground research laboratory Continuous transmissivity measurements record self‐sealing inside a clay‐rich fault zone Transmissivity undergoes a phase of domination by slow plastic compaction and shearing during the initial post‐activation period, with mineral swelling exerting its influence over the long term

Guglielmi, Yves↗

A role for subducting clays in the water transportation into the Earth’s lower mantle

Subducting sedimentary layer typically contains water and hydrated clay minerals. The stability of clay minerals under such hydrous subduction environment would therefore constraint the lithology and physical properties of the subducting slab interface. Here we show that pyrophyllite (Al 2 Si 4 O 10 (OH) 2 ), one of the representative clay minerals in the alumina-silica-water (Al 2 O 3 -SiO 2 -H 2 O, ASH) system, breakdowns to contain further hydrated minerals, gibbsite (Al(OH) 3 ) and diaspore (AlO(OH)), when subducts along a water-saturated cold subduction geotherm. Such a hydration breakdown occurs at a depth of ~135 km to uptake water by ~1.8 wt%. Subsequently, dehydration breakdown occurs at ~185 km depth to release back the same amount of water, after which the net crystalline water content is preserved down to ~660 km depth, delivering a net amount of ~5.0 wt% H 2 O in a phase assemblage containing δ-AlOOH and phase Egg (AlSiO 3 (OH)). Our results thus demonstrate the importance of subducting clays to account the delivery of ~22% of water down to the lower mantle.

58 GEOSCIENCES↗

Mathematical modelling of undrained clay behavior

The proposed general analytical model describes the anisotropic, elastoplastic, path-dependent, stress-strain properties of inviscid saturated clays under undrained conditions. Model parameters are determined by using results from strain-controlled simple shear tests on a saturated clay. The model's accuracy is evaluated by applying it to predict the results of other tests on the same clay, including monotonic and cyclic loading. The model explains the very anisotropic shear strength behavior observed for weak marine clays.

Prevost, J. H.↗

Alteration of glass as a possible source of clay minerals on Mars

Thermodynamic calculations show that, under present Martian surface conditions, favorable gas-solid weathering products of feldspar glasses should include beidellites (clays of the montmorillonite series) + carbonates + quartz. The gas-solid weathering of mafic silicate glass ( of volcanic or impact origin) may similarly favor the production of metastable Fe-rich montmorillonite clays. Simple mass-balance calculations suggest that gas-solid weathering of Martian proto-regolith containing 10% glass could conceivably produce a global blanket of clays at a rate of at least 0.4 cm/b.y. The production rate should be expected to increase significantly with the glass content and rate of reworking of the proto-regolith and with the availability of water. Complete extraction of altered glass from a lunar-like proto-regolith might yield a global Martian clay blanket about 10-100 cm in thickness.

Gooding, J. L.↗

Enhancement of peptide bond formation by polyribonucleotides on clay surfaces in fluctuating environments

The selective effects of polyribonucleotides on the formation of glycine peptide bonds in glycine on clay surfaces are investigated as a model for a template mechanism for the effects of polynucleotides on peptide bond formation. Free oligoglycine yields were determined for the cycling reaction of glycine in the presence and absence of clay and polyribonucleotides or polydeoxyribonucleotides. The polyribonucleotides are observed to lead to increases of up to fourfold increases in oligoglycine formed, with greater enhancements for poly-G nucleotides than for poly-A, poly-U and poly-C, indicating a codonic bias. Polydeoxyribonucleotides are found to provide no enhancement in peptide formation rates, and yields were also greatly reduced in the absence of clay. A mechanism for peptide synthesis is proposed which involves the activation of glycine on the clay surface, followed by the formation of esters between glycine and the 2-prime OH groups of the polyribonucleotide and peptide bonds between adjacent amino acyl esters. It is pointed out that if this mechanism is correct, it may provide a basis for a direct template translation process, which would produce a singlet genetic code.

White, D. H.↗

First Direct Detection of Clay Minerals on Mars

Magnesian clays or clay-type minerals were conclusively detected in the martian regolith. Near-IR spectral observations of Mars using the Mauna Kea 2.2-m telescope show weak but definite absorption bands near microns. The absorption band positions and widths match those produced by combined OH stretch and Mg-OH lattice modes and are diagnostic of minerals with structural OH such as clays and amphiboles. Likely candidate minerals include serpentine, talc, hectorite, and sponite. There is no spectral evidence for aluminous hydroxylated minerals. No distinct band occurs at 2.55 microns, as would be expected if carbonates were responsible for the 2.35 micron absorption. High-albedo regions such as Elysium and Utopia have the strongest bands near 2.35 microns, as would be expected for heavily weathered soils. Low-albedo regions such as Iapygia show weaker but distinct bands, consistent with moderate coatings, streaks, and splotches of bright weathered material. In all areas observed, the 2.35-micron absorption is at least three times weaker than would be expected if well-crystallized clay minerals made up the bulk of bright soils on Mars.

Singer, R. B.↗

pH profile of the adsorption of nucleotides onto montmorillonite. I - Selected homoionic clays

The effect of pH and adsorbed ions on the adsorption of purine and pyrimidine nucleotides on montmorillonite clay was studied experimentally. The specific nucleotides examined were: 5 prime-AMP; 3-prime AMP; and 5 prime-CMP. The pH of the clay samples was adjusted to various levels in the 2-12 pH range using microliter volumes of concentrated acid (1N HCl) and base (1NHNaOH). It was found that preferential adsorption among nulceotides was dependent on the pH level and on the characteristics of the substituted metal cation and anion exchange mechanisms. Below pH 4, adsorption was attributed to cation and anion exchange mechanisms. Above pH 4, however, adsorption was attributed to the complexation mechanisms occurring between the metal cations in the clay exchange site and in the biomolecule. The possible role of homoionic clays in the concentration mechanisms of biomonomers in the prebiotic environment is discussed.

Lawless, J. G.↗

Mineral catalysis of the formation of the phosphodiester bond in aqueous solution - The possible role of montmorillonite clays

The possible role of montmorillonite clays in the spontaneous formation on the primitive earth of the phosphodiester bond in the presence of water was investigated in experiments measuring the binding of various nucleosides and nucleotides with Na(+)-montmorillonite 22A and the reactions of these compounds with a water-soluble carbodiimide. It was found that, at neutral pH, adenine derivatives bind stronger than the corresponding uracil derivatives, consistent with the protonation of the adenine by the acidic clay surface and a cationic binding of the protonated ring to the anionic clay surface. The reaction of the 5-prime-AMP with carbodiimide resulted in the formation of 2-prime,5-prime-pApA (18.9 percent), 3-prime,5-prime-pApA (11 percent), and AppA (4.8 percent). The yields of these oligomers obtained when poly(U) was used in place of the clay were 15.5 percent, 3.7 percent, and 14.9 percent AppA, respectively.

Ferris, James P.↗

Dibenzo-p-dioxins in the environment from ceramics and pottery produced from ball clay mined in the United States

Processed ball clay samples used in the production of ceramics and samples of the ceramic products were collected and analyzed for the presence and concentration of the 2,3,7,8-Cl substituted polychlorinated dibenzo-p-dioxins and -furans (PCDDs/PCDFs). The processed ball clay had average PCDD concentrations of 3.2 ng/g toxic equivalents, a congener profile, and isomer distribution consistent with those found previously in raw ball clay. The PCDF concentrations were below the average limit of detection (LOD) of 0.5 pg/g. The final fired ceramic products were found to be free of PCDDs/PCDFs at the LODs. A consideration of the conditions involved in the firing process suggests that the PCDDs, if not destroyed, may be released to the atmosphere and could represent an as yet unidentified source of dioxins to the environment. In addition, the PCDDs in clay dust generated during manufacturing operations may represent a potential occupational exposure.

Aluminum Silicates/chemistry↗

The Use 0f AVIRIS Imagery To Assess Clay Mineralogy And Debris-Flow Potential In Cataract Canyon, Utah: A Preliminary Report

Worldwide debris flows destroy property and take human lives every year (Costa, 1984). As a result of extensive property damage and loss of life there is a pressing need to go beyond just describing the nature and extent of debris flows as they occur. Most of the research into debris-flow initiation has centered on rainfall, slope angle, and existing debris-flow deposits (Costa and Wieczorek, 1987). The factor of source lithology has been recently addressed by studies in the sedimentary terranes of Grand Canyon (Webb et al., 1996; Griffiths et al., 1996) and on the Colorado Plateau as a whole.3 On the Colorado Plateau shales dominated by kaolinite and illite clays are significantly more likely to be recent producers of debris-flows than are shales in which smectite clays dominate.3 Establishing the location of shales and colluvial deposits containing kaolinite and illite clays in sedimentary terranes on the Colorado Plateau is essential to predicting where debris flows are likely to occur. AVIRIS imagery can be used to distinguish between types of clay minerals (Chabrillat et al., 2001), providing the basis for surface-materials maps. The ultimate product of this study will be a model that can be used to estimate the debris-flow hazard in Cataract Canyon, Utah. This model will be based on GIS overlay analysis of debris-flow initiation factor maps, including surface-materials maps derived from AVIRIS data.

Rudd, Lawrence↗

Investigation of the Glen Torridon Clay-Bearing Unit and Overlying Greenheugh Pediment by the Sample Analysis at Mars Instrument Suite

Exploring the Glen Torridon (GT) clay-bearing unit in Gale crater has long been a prime goal for the Mars Science Laboratory (MSL) because of spectral signatures of smectite identified from orbit. Smectite clay minerals can indicate habitable environments [1,2] and possibly facilitate the preservation of organic compounds [e.g., 3-7].Also, sulfate-bearing layers overlie GT and this sequence may record a large-scale change in aqueous conditions overtime [8].The Sample Analysis at Mars (SAM) instrument suitehas been essential in understanding volatile-bearing phases in Gale crater materials. SAM EGA has detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases, including organic fragments, evolved from many samples on heating. The identity and evolution temperature of evolved gases can support mineral detection by CheMin instrument X-ray diffraction (XRD)and place constraints on trace volatile-bearing phases, clay mineral compositions, and X-ray amorphous materials. In GT, SAM analyzed the sample Kilmarie (KM) from the Jura member, Glen Etive (GE), Mary Anning (MA) and Groken (GR)from the Knockfarril Hill member (KHm), Glasgow (GG) and Hutton (HU) from the fractured Intermediate Unit (fIU), and Edinburgh (EB) from the Stimson formation rocks of the Greenheugh Pediment (GP). The Jura, KHm and fIU are all members of the Murray formation. HU was sampled near the basal Siccar Point group (SPg) unconformity between the fIU and GP, in an area that exhibits a brighter tone and differences in geochemistry compared to Murray materials down-section [9,10]. CheMin XRD of most samples (except for HU and EB)showed large abundances of smectite clay minerals (~25-35%) and all samples showed X-ray amorphous materials and relatively low amounts of well-crystalline hematite[11]. SAM evaluated mineralogy through evolved gas analysis mass spectrometry (EGA) while detailed organic chemistry of several samples was examined by pyrolysis gas chromatography mass spectrometry and wet chemistry experiments [12,13].Here we discuss data and interpretations from SAM EGA analyses.

Mars↗

Oxidation of biogenic U(IV) mediated by iron-bearing clay minerals, iron-reducing bacteria, and organic ligands

Bioreduction of hexavalent uranium (U(VI)) to tetravalent uranium (U(IV)) by dissimilatory metal-reducing bacteria (DMRB) is considered an effective strategy for uranium immobilization in contaminated environments. However, U(IV) can be reoxidized to U(VI) under fluctuating redox conditions and remobilized. This work investigates the oxidation behavior of biogenic U(IV) in the presence of bioreduced iron-bearing clay minerals (rNAu-2), iron-reducing bacteria (Shewanella putrefaciens CN32), and organic ligands (ethylenediaminetetraacetic acid (EDTA) and citrate). Results demonstrate that the presence of CN32 significantly inhibits U(IV) oxidation. rNAu-2 exerted a context-dependent influence on U(IV) oxidation: its effect was masked by bicarbonate-promoted U(VI) mobilization in the absence of active CN32, but became detectable when CN32-mediated microbial protection slowed U(IV) oxidation. EDTA and citrate markedly accelerate U(IV) oxidation via formation of soluble U(IV)-ligand complexes, changing U(IV) redox potentials, and by promoting clay mineral dissolution that enhances Fe(II)/Fe(III) redox cycling. Collectively, our findings constrain the roles that clay minerals, iron-reducing bacteria, and organic ligands play in governing U(IV) stability, emphasizing the need to account for these factors in developing robust bioremediation strategies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

A comparative analysis of numerical approaches for the description of gas flow in clay-based repository systems: From a laboratory to a large-scale gas injection test

There is nowadays a consensus among many countries that geological disposal is a favourable solution for the long-term management. Although different host formations and different barrier systems are under consideration around the world, clay-based materials form an important component for waste isolation in most national programmes. Hence, a good comprehension of the effect of gas flow on the hydro-mechanical behaviour of clay-based soils is essential, both at laboratory and field scale. Task B under the international cooperative project DECOVALEX-2023 has recently shown that, after some enhancement, models can be employed to reproduce laboratory scale tests, even with different sample geometries 37 . However, further work is required to understand whether they can be applied to simulate a large-scale experiment. Up-scaling of models for the advective transport of gas through clay-based low permeable material presents a number of problems related to the difficulty in obtaining consistent hydrogeological parameters and constitutive relationships at both laboratory and field scale. Based on a unique dataset from a large-scale gas injection test (Lasgit) performed at the Äspö Hard Rock Laboratory (Sweden), Task B within DECOVALEX-2023 has explored the refinement of these numerical strategies applied to the simulation of gas flow. Work performed within the task reveals that codes do not need to be substantially modified from the laboratory models to reproduce full-scale tests: indeed, model parameters calibrated and validated at laboratory scale have been applied to predict field scale gas flow at Lasgit, including peak gas pressure and injected cumulative gas volume. By means of (1) the introduction of interfaces between blocks to reflect the experimental configuration and the (2) adjustment of some parameters (e.g., higher permeability), the updated models are able to represent most of the key features observed in the experimental data, even at a large scale.

Tamayo-Mas, E↗

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↗

The influence of various cations on the catalytic properties of clays

The polymerization of alanine adenylate in the presence of the sodium form of various clays was studied, and hectorite was found to cause more polymerization than nontronite and montmorillonite (in that order) although the differences were not great. The effect on polymerization of presaturating montmorillonite with different cations was determined. Hectorite, with increased basicity of the interspatial planes, allows polymerization of lysine, which montmorillonite does not. The general trend is that, for the same amino acid, higher degrees of polymerization are obtained when the cation in the octahedral lattice of the clay is divalent rather than trivalent. With the exchangeable cations the order is reversed, for a reason that is explained. The main role of clays in the polymerization mechanism of amino acids is concentration and neutralization of charges.

Paecht-Horowitz, M.↗