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At least 145 records · Page 8

High-resolution analysis of clay minerals and amorphous materials in martian analog environments

Mudrocks and mud-sized sediments (i.e., silt to clay) dominate the surface of Earth and Mars. These fine-grained sediments preserve a rich history of sedimentary processes from source to sink and shed light on ancient climates. However, both the physical and chemical nature of these materials make them difficult to fully characterize with traditional laboratory techniques. Here, we explore a cross-disciplinary and high-resolution approach using synchrotron radiation for X-ray diffraction, pair distribution function analysis, and submicrometer-scale X-ray fluorescence, combined with transmission electron microscopy, to better understand the nanostructure and composition of mud-sized sediments from a glacio-fluvial watershed in southwest Iceland. Our results demonstrate that sediments in the cold and wet climate of Iceland are more altered than previously thought, as evidenced by the identification of kaolinite and mixed-layer kaolinite-smectite. Additionally, sediments are enriched in amorphous materials and nanocrystalline phases, as determined from grain morphologies and compositions consistent with allophane, hisingerite, ferrihydrite, and halloysite. These alteration products are present as intimate mixtures that vary across depositional sites, demonstrating the dynamic nature of the secondary assemblage from source to sink. This work has implications for Mars, where, for example, basalt-sourced sedimentary rocks from Gale crater are abundant in clay minerals and amorphous materials. Finally, this work underpins the importance of using high-resolution techniques, a coordinated methodology, and developing innovative approaches for future planetary sample return missions (e.g., Mars sample return).

36 MATERIALS SCIENCE↗

The Sealing Mechanisms of a Fracture in Opalinus Clay as Revealed by in situ Synchrotron X-Ray Micro-Tomography

The detailed mechanisms of the sealing of a single fracture, from hydration to almost complete closure by increase of confining pressure, as monitored from in situ synchrotron X-ray microtomography during the flow of carbonated water, is here shown for the first time. Different mechanisms play the key role at different stages in the evolution of the fracture. Hydration mechanically weakens the surfaces of the fracture and induces a first closure due to microcracking at the asperity contacts, increasing their size and creating choke points. Increase in confining stress promptly hydraulically seals the fracture by closing the main choke point, with a relative small deformation of the sample. Finally, the more pervasive mechanical deformation observed at higher stresses almost completely seals the whole fracture. The evolution of the sample has been described and quantified using 4D image processing, focusing on the evolution of aperture and digital volume correlation. Hydraulic properties of the sample at different stages have been modeled via Stokes flow simulation, and the results compared to the morphometric analysis, finding positive correlations with the average fracture aperture variation along the flowpath in function of confining pressure. Opalinus Clay is found to be a rock markedly prone to sealing in case of flow with carbonated water; this behavior is the result of the large fraction of clays and of its microstructure, lacking both cementing phases and large stiff particles. CO2 in this sample has no evident role in the evolution of the fracture; chemically induced weathering on the surface has not been detected, in contrast with the behavior observed in samples with carbonates as cementing phase.

58 GEOSCIENCES↗

The hydration, microstructure, and mechanical properties of vaterite calcined clay cement (VC 3 )

Limestone (calcite) calcined clay cement (LC 3 ) is a promising low-CO 2 binder, but the low activity of calcite cannot compensate the reduction in clinker factor, resulting in low one-day strength and limiting its broad applications. As recent carbon capture and utilization technologies allow scalable production of vaterite, a more reactive CaCO 3 polymorph, we overcome the challenge by introducing vaterite calcined clay cement (VC 3 ), inspired by the vaterite-calcite phase change. In the present study, VC 3 exhibits higher compressive strengths and faster hydration than LC 3 . Compared to hydrated LC 3 , hydrated VC 3 exhibits increased amount of hemi- and mono-carboaluminate formation and decreased amount of strätlingite formation. With gypsum adjustment, the 1-day strength of VC 3 is higher than that of pure cement reference. Finally, VC 3 , a low-CO 2 binder, presents great potential as a host of the metastable CaCO 3 for carbon storage and utilization and as an enabler of carbon capture at gigaton scales.

36 MATERIALS SCIENCE↗

Coupled feldspar dissolution and secondary mineral precipitation in batch systems: 6. Labradorite dissolution, calcite growth, and clay precipitation at 60 °C and pH 8.2–8.4

Here, we conducted experiments on concurrent labradorite dissolution, calcite precipitation, and clay precipitation in batch reactor systems and tracked reaction processes using multiple isotope tracers. Labradorite was chosen for its role as a major and reactive component in basalt; the experiments thus directly impact our understanding of CO 2 storage in basalt aquifers and enhanced rock weathering. We doped initial solutions with 29 Si, 43 Ca, and Ca 13 CO 3 (s). Experiments were conducted at 60 °C and pH ~ 8.3 for up to 840 h, with isotope ratios in the experimental aqueous solutions measured using MC-ICP-MS. Unidirectional rates of labradorite dissolution near equilibrium were approximately two orders of magnitude slower than far-from-equilibrium rates reported in the literature. Calcite growth occurred near equilibrium and the rates were limited by the labradorite dissolution rates. In the steady state phase, the interplay of these three heterogeneous reactions—labradorite dissolution, calcite growth, and clay precipitation—results in a coupled system that approaches a near-equilibrium state. The system does not reach true equilibrium because labradorite continues to dissolve, albeit at a much slower rate near equilibrium. The overall reaction can be approximated as, Na 0.4 Ca 0.6 Al 1.6 Si 2.4 O 8 + 0.6HCO 3 - + 1·.7H 2 O + 0.4H + → 0.4Na + + 0.6CaCO 3(s) + 0.5Al 2 Si 2 O 5 (OH) 4(s) + 0.6Al(OH) 4 - + 1.4SiO 2 o (aq). The experimental results show that using short-term far-from-equilibrium rate constants would lead to an overestimation of feldspar weathering rates at the Earth’s surface (e.g., basalt weathering and enhanced rock weathering) and CO 2 mineralization in basalt aquifers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lithological controls on soil geochemistry and clay mineralogy across Spodosols in the coastal temperate rainforest of southeast Alaska

The interaction of similar soil forming factors with different parent materials determines soil chemical weathering, influencing soil processes and properties. In the coastal temperate rainforests of southeast Alaska, Spodosols is the dominant soil order in well-drained parent materials regardless of the lithology. Yet, the role of lithology on chemical weathering, base cation depletion, and mineral transformation during pedogenesis remains elusive. Here, we established a lithosequence comprised of soils derived from tonalite, phyllite, slate, and metavolcanic rocks to test the hypothesis that despite the soils in southeast Alaska presenting similar taxonomy and morphology, the influence of lithology in chemical weathering intensity and mineralogy can be detected. We evaluated physicochemical properties, clay mineralogy, Fe-Al oxides, chemical weathering, and elemental mass balance on eleven Spodosols sampled along the lithosequence. We also propose a new weathering index, the Weathering Index for Spodosols (WISP), suitable to evaluate the weathering degree of soils with Al mobility and base-rich parent materials. This index fills a gap in traditional weathering indices that uses Al as an immobile element and/or does not evaluate the leaching of main base cations. We found the pedons across the lithosequence expressed similar physicochemical properties, with predominantly thick profiles, presenting andic properties, relatively thick spodic horizons, and thin E horizons. Podzolization imposed similar mineral transformation trends, mainly dissolution of chlorite, mica alteration to interstratified mica-vermiculite, and formation of smectite in E horizons. Kaolinite was detected in the soils from all lithologies, but only in trace amounts in phyllite soils. Fe oxides depth distribution was similar but with a higher concentration in the slate (44.5 ± 4.2 g/kg), followed by metavolcanic (31.6 ± 4.0 g/kg), phyllite (27.9 ± 3.8 g/kg), and tonalite soils (19.9 ± 5.7 g/kg) and predominantly as organometallic complexes (extracted by Na-pyrophosphate). The stronger weathering of chlorite and mica in the E horizons was reflected in larger losses of Mg and K, while Ca and Na were more depleted in the spodic horizons, suggesting plagioclase weathering. Slate soils were the most depleted in base cations, followed by phyllite, tonalite, and metavolcanic soils. The more depleted status of slate soils was supported by the higher WISP values (WISP = 62), followed by phyllite (WISP = 55), tonalite (WISP = 53), and metavolcanic soils (WISP = 45). Our results demonstrated that lithology controlled elemental depletion intensities, Fe oxide concentrations, and partially the clay fraction mineralogy in addition to podzolization acting as a dominant pedogenic process across all sites. These findings advance our understanding of the role of lithology on soil mineralogy/geochemistry that impacts critical soil functions, such as the soil carbon cycle, elemental fluxes, organo-mineral interactions, and solid-solution reactions.

54 ENVIRONMENTAL SCIENCES↗

Greenhouse Gas Emissions and Decarbonization Potential of Global Fired Clay Brick Production

Fired clay bricks (FCBs) are a dominant building material globally due to their low cost and simplicity of production, especially in low- and middle-income countries. With a projected rising housing demand, commensurate growth in brick demand is anticipated, the production of which could result in significant greenhouse gas (GHG) emissions. Robust models are needed to estimate brick demand and emissions to systematically address decarbonization pathways. Few sources report production values; hence, we present two novel proxy models: (i) a consumption prediction model, relying on country-specific clay extraction data, dynamic building stock modeling, and average material intensity use allowing for projections to 2050; and (ii) a GHG emissions model, using literature-based data and production technology-specific inputs. Based on these models, the current global FCB consumption is estimated as 2.18 Gt annually, resulting in approximately 500 million tCO2e (1% of current global GHG emissions). If unaddressed, this fraction could increase to 3.5-5% in 2050 considering a moderate SSP 2-4.5 climate change mitigation scenario. Consequently, we explored three potential decarbonization pathways: (i) improving energy efficiency; (ii) shifting production to best practices; and (iii) replacing half of FCB demand with hollow concrete blocks, resulting in 27%, 49%, and 51% reduction in GHG emissions, respectively.

Olsson, Josefine A↗

Carbon–Mineral Slurry Electrodes for Energy-Efficient Lithium Leaching from Low-Grade Clay Feedstocks

Lithium extraction from clay deposits is typically hampered by low lithium grades and the high capital and energy demands of conventional processing. We report an ambient temperature electrochemical leaching method that bypasses high-temperature roasting and concentrated-acid leaching, directly liberating 93% of lithium from low-grade hectorite in 24 h at 1 V, with 77% Faradaic efficiency, an energy intensity of 3.91 MWh/t lithium carbonate equivalent (LCE). Utilizing a carbon-mineral composite slurry electrode strategy we achieve electron-driven lattice deconstruction through iron oxidation coupled with proton uptake to drive lithium deintercalation, offering a new strategy for low-temperature critical-metal recovery. A preliminary cost analysis highlights pathways to achieving cost intensities below $3000/t LCE. Challenges remain in improving current density, extraction kinetics, and demonstrating process scalability, however, this work establishes a foundation for effective electrochemical lithium extraction from abundant but previously uneconomical clay deposits.

Haddad, Andrew Z↗

Control of Structural Hydrophobicity and Cation Solvation on Interlayer Water Transport during Clay Dehydration

Swelling clay hydration/dehydration is important to many environmental and industrial processes. Experimental studies usually probe equilibrium hydration states in an averaged manner and thus cannot capture the fast water transport and structural change in interlayers during hydration/dehydration. Using molecular simulations and thermogravimetric analyses, we observe a two-stage dehydration process. The first stage is controlled by evaporation at the edges: water molecules near hydrophobic sites and the first few water molecules of the hydration shell of cations move fast to particle edges for evaporation. The second stage is controlled by slow desorption of the last 1–2 water molecules from the cations and slow transport through the interlayers. The two-stage dehydration is strongly coupled with interlayer collapse and the coordination number changes of cations, all of which depend on layer charge distribution. Furthermore, this mechanistic interpretation of clay dehydration can be key to the coupled chemomechanical behavior in natural/engineered barriers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evolution of Elastic and Mechanical Properties During Fault Shear: The Roles of Clay Content, Fabric Development, and Porosity

Phyllosilicates weaken faults due to the formation of shear fabrics. Although the impacts of clay abundance and fabric on frictional strength, sliding stability, and porosity of faults are well studied, their influence on elastic properties is less known, though they are key factors for fault stiffness. We document the role that fabric and consolidation play in elastic properties and show that smectite content is the most important factor determining whether fabric or porosity controls the elastic response of faults. We conducted a suite of shear experiments on synthetic smectite-quartz fault gouges (10–100 wt% smectite) and sediment incoming to the Sumatra subduction zone. We monitored Vp, Vs, friction, porosity, shear and bulk moduli. We find that mechanical and elastic properties for gouges with abundant smectite are almost entirely controlled by fabric formation (decreasing mechanical and elastic properties with shear). Though fabrics control the elastic response of smectite-poor gouges over intermediate shear strains, porosity is the primary control throughout the majority of shearing. Elastic properties vary systematically with smectite content: High smectite gouges have values of Vp ~ 1,300–1,800 m/s, Vs ~ 900–1,100 m/s, K ~ 1–4 GPa, and G ~ 1–2 GPa, and low smectite gouges have values of Vp ~ 2,300–2,500 m/s, Vs ~ 1,200–1,300 m/s, K ~ 5–8 GPa, and G ~ 2.5–3 GPa. We find that, even in smectite-poor gouges, shear fabric also affects stiffness and elastic moduli, implying that while smectite abundance plays a clear role in controlling gouge properties, other fine-grained and platy clay minerals may produce similar behavior through their control on the development of fabrics and thin shear surfaces.

58 GEOSCIENCES↗

Low hydrogen solubility in clay interlayers limits gas loss in hydrogen geological storage

Gas intercalation into clay interlayers may result in hydrogen loss in the geological storage of hydrogen; a phenomenon that has not been fully understood and quantified. Here we use metadynamics molecular simulations to calculate the free energy landscape of H 2 intercalation into montmorillonite interlayers and the H 2 solubility in the confined water; in comparison with results obtained for CO 2 . Furthermore, the results indicate that H 2 intercalation into hydrated interlayers is thermodynamically unfavorable while CO 2 intercalation can be favorable. H 2 solubility in hydrated clay interlayers is in the same order of magnitude as that in bulk water and therefore no over-solubility effect due to nanoconfinement is observed – in striking contrast with CO 2 . These results indicate that H 2 loss and leakage through hydrated interlayers due to intercalation in a subsurface storage system, if any, is limited.

58 GEOSCIENCES↗

Surface Complexation/Ion Exchange Hybrid Model for Radionuclide Sorption to Clay Minerals (M4SF-23LL010301062)

This progress report (Level 4 Milestone Number M4SF-23LL010301062) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Argillite International Collaborations Activity Number SF-23LL01030106. The activity is focused on our long-term commitment to engaging our partners in international nuclear waste repository research. The focus of this milestone is the establishment of international collaborations for surface complexation modeling and the associated impacts of unlocking larger, community-based datasets. More specifically, we are developing a database framework for Spent Fuel and Waste and Science Technology (SFWST) that is aligned with the Helmholtz Zentrum Dresden Rossendorf (HZDR) sorption database development group in support of the database needs of the SFWST program. In our FY22 effort, we described a detailed analysis of U(VI) sorption to quartz through both traditional surface complexation modeling and through a hybrid ML framework. In FY23, effort was placed on publication of these results and expansion of the LLNL surface complexation and ion exchange database (L-SCIE) in order to assess mineral-based radionuclide retardation under a wider variety of geochemical conditions (e.g., ionic strength, varying electrolyte compositions). Efforts were initiated to expand L-SCIE to include radionuclide surface complexation and ion exchange to clays that are relevant to subsurface geochemical processes occurring at nuclear waste repositories. In particular, a large source of sorption data for clays resides at the Paul Scherrer Institute (PSI) (work primarily by Bradbury and Baeyens) and we initiated discussions on how to retrieve those data and apply FAIR principles to those datasets. In addition to L-SCIE development, two hybrid models that incorporate AI/ML were investigated and compared to discern the most promising approaches for accurate and precise estimations of radionuclide retardation. Key considerations for future model development include (1) the ability to reduce computational burden on determining retardation coefficients for PA and (2) the ability to quantify and predict radionuclide-mineral partitioning at a more efficient, rapid pace due to automated workflows. Upon the careful consideration of the most effective modeling approaches, we are identifying ways to implement these approaches into PA. Ultimately, the data science-based workflows will provide a major incentive for other institutions to adopt a FAIR-formatted, interoperable database. LLNL will play a key role in disseminating sorption data and acting as good data stewards by updating the database in a consistent format and assessing the quality of the newly assimilated data in an organized fashion. To this end, all data and workflows are open access and made available on the LLNL Seaborg research website (https://seaborg.llnl.gov/resources/geochemical-databases-modeling-codes).

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Low-temperature oxygen-plasma effects on surveyor plasmo-clay coating

The objective was to determine whether the reflectance of the degraded plasmo-clay thermal control coating could be restored by exposing it to an oxygen plasma. An experiment was conducted to determine whether bulk radiation damage would be removed by a reabsorption of oxygen ions into the pigment crystal lattice. Results show that the oxygen plasma treatment can eliminate some of the lunar environment-induced degradation on the plasmo-clay coating. Visual observations of the lunar soil on the surface after plasma treatment indicated that it was still highly absorbent to light. Therefore, part of the residual discoloration could be due to lunar soil.

Gillette, R. B.↗

Ultrafiltration by a compacted clay membrane. I - Oxygen and hydrogen isotopic fractionation. II - Sodium ion exclusion at various ionic strengths.

Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disk compacted to a porosity of 35% by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5% and in O-18 by 0.8% relative to the residual solution. No additional isotopic fractionation due to a salt-filtering mechanism was observed at NaCl concentrations up to 0.01N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. It is shown how it is possible to proceed from the ion exchange capacity of clay minerals and, by means of the Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane.

Coplen, T. B.↗

The formation of goethite and hydrated clay minerals on Mars

Laboratory studies reported by Huguenin (1973) on the kinetics and mechanism of the photostimulated oxidation of magnetic and preliminary laboratory data on the weathering of silicates, reported herein, are applied to Mars. Basalts in the Martian dark areas are predicted to alter to hydrated Fe(2 plus or minus) depleted clay minerals, minor goethite, and minor to trace amounts of transition metal oxides such as TiO2, MnO2, and Cr2O3 at a rate of 10 to the minus 1.5 plus or minus 1.5 micron/yr. Some Ca-Mg carbonates are also expected to be formed. The clay minerals are predicted to be more silica-rich than the silicate source material, SiO2 contents of 60% or higher being expected, and strongly depleted in Fe(2+). The oxygen, OH, and H2O contents of the bulk weathering product are predicted to be significantly greater than those of the dark-area source materials, whereas the relative bulk metal abundances should be the same.

Huguenin, R. L.↗

Clay catalyzed polymerization of amino acid adenylates and its relationship to biochemical reactions

The adsorption and polymerization of alanine adenylate on montmorillonite at pH 7 when either its interspacial faces or its edger are blocked by an excess of histidine or sodium hexametaphosphate was investigated. Results indicate that alanine adenylate can be adsorbed any place on the interspacial spaces of the clay; however, adsorption of its phosphate part, which is limited to the edges of the clay, is necessary for polymerization to occur. As a result, polymerization takes place only at sites on the interspacial faces bordering the edges.

Paecht-Horowitz, M.↗

Silt-clay aggregates on Mars

Viking observations suggest abundant silt and clay particles on Mars. It is proposed that some of these particles agglomerate to form sand size aggregates that are redeposited as sandlike features such as drifts and dunes. Although the binding for the aggregates could include salt cementation or other mechanisms, electrostatic bonding is considered to be a primary force holding the aggregates together. Various laboratory experiments conducted since the 19th century, and as reported here for simulated Martian conditions, show that both the magnitude and sign of electrical charges on windblown particles are functions of particle velocity, shape and composition, atmospheric pressure, atmospheric composition and other factors. Electrical charges have been measured for saltating particles in the wind tunnel and in the field, on the surfaces of sand dunes, and within dust clouds on earth. Similar, and perhaps even greater, charges are proposed to occur on Mars, which could form aggregates of silt and clay size particles

Greeley, R.↗

The possible role of metal ions and clays in prebiotic chemistry

Eight homoionic bentonites were prepared using alkali, alkaline earth, and transition metal ions as counterions. The interaction of the clays with 5'-AMP was studied and it was found that the alkali metal-substituted clays did not remove any nucleotide from dilute solution, and that zinc-bentonite adsorbed the most (98%). In addition, study of the interaction of seven other nucleotides with zinc-bentonite showed that the purine nucleotides were more strongly absorbed than the pyrimidine nucleotides. Langmuir isotherms were obtained for these systems and the adsorption data were explained by the adsorption coefficient and the accessibility of metal for binding.

Lawless, J. G.↗

A possible role of fluctuating clay-water systems in the production of ordered prebiotic oligomers

A model is proposed for the intermediate stages of prebiotic evolution, based on the characteristics of the adsorption and condensation of amino acids and nucleotides on the surface area of clay minerals in a fluctuating environment. Template replication and translation of adsorbed oligonucleotides and catalytic effects by peptide products on further condensation are proposed, due to specific properties of hypohydrous clay surfaces as well as the biomolecules themselves. Experimental evidence supports some of the proposed interactions, and all of them can be tested experimentally.

Lahav, N.↗