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Life support systems research at the Johnson Space Center

The bioregenerative life support systems research at Johnson Space Center focuses on the use of lunar regolith as a plant growth medium. Current dissolution experiments are being conducted to ascertain the response of lunar regolith to various solvents and weathering environments. The transformation of lunar minerals into minerals such as zeolites which would be more conducive to plant growth is also investigated. A study is currently underway to examine the ability of zeolite/apatite mixtures to provide N, P, and K through dissolution and ion exchange. The development and characterization of simulated lunar regolith for preliminary experimentation are also discussed. The life support systems technology used on the Mercury, Gemini, Apollo, and Shuttle missions is reviewed and current research on regenerative life support systems technology for potential use in Space Station Freedom is discussed.

Henninger, D. L.↗

Facet-dependent growth and dissolution of hematite resulting from autocatalytic interactions with Fe(II) and oxalic acid

The ability to simultaneously monitor the flux of iron atoms within the solution and solid phases can provide considerable insight into mechanisms of iron oxide mineral transformations. The autocatalytic interaction between hematite and Fe(II)-oxalate has long been of interest for its environmental and industrial relevance. In this study we take advantage of iron isotopic labelling and mass-sensitive imaging at the single particle scale to determine how changes in solution composition correlate with the morphologic evolution of faceted, micrometer-sized hematite platelets. Net dissolution is confirmed through analyses of aqueous iron chemistry, as well as by quantitative atomic force microscopy. Isotopic mapping techniques show that Fe(II) readily adsorbs to (001) and (012) surfaces in the absence of oxalate, but when oxalate is present selective dissolution of the (001) surface prevails and 57Fe deposition via recrystallization is not observed. Comparison between particle microtopographies following reaction with Fe(II), oxalate, and Fe(II)-oxalate show substantially different behavior, consistent with distinct mechanisms of interaction with hematite surfaces. The extensive characterization conducted on the coupled solution/solid dynamics in this system provides new insight for distinguishing crystal growth, dissolution, and recrystallization processes.

Taylor, Sandra D. [BATTELLE (PACIFIC NW LAB)]↗

Mechanistic understanding of carbon mineralization in fracture systems using microfluidics

Carbon mineralization in mafic and ultramafic rocks presents an opportunity for permanent carbon storage in the Earth's subsurface. However, due to their lower permeability, pre-existing fracture networks are key for mineralization to occur. Therefore, to fully develop this technology, a mechanistic understanding of the mineralization behavior in fractures with the consideration of hydrodynamic components is required. We use high-pressure microfluidics to investigate key mechanisms influencing dissolution–precipitation in a fracture network. The experiments were conducted in micromodels made of natural rocks with a comb-shaped flow channel to mimic a fracture network. This enabled studying the effect of injection rate on coupled dissolution–precipitation in advection and diffusion-dominated flow paths. We used gypsum carbonation as an analog reaction to allow for realistic experimental time frames due to its rapid reaction kinetics. The experimental work is coupled with high-fidelity numerical simulations to enhance our understanding of the parameters affecting the mineralization reaction. Our results demonstrate the importance of flow rate on the rate and nature of the gypsum carbonation reaction revealing that higher flow rates enable deeper penetration of the mineral precipitation front into the dead-end channels. This is an important finding since for sustained mineralization in a fracture network, precipitation in dead-ends while still allowing for flowing fractures is critical. Detailed characterization of the precipitates showed that lower flow rates led to porous and loose precipitates in the form of aragonite while higher flow rates mimicked supersaturation behavior leading to the formation of calcite. The reactive transport simulations further demonstrated the significance of flow velocity in advection-dominated channels to influence the efficiency of carbon mineralization in diffusion-dominated channels, potentially clogging of dead-end channels. These findings highlight the need for coupling chemical, mechanical, and hydrodynamic processes to evaluate the nature and extent of carbon mineralization in fractured media critical for permanent storage in mafic and ultramafic formations. This research further highlights the need for more investigation in potential subsurface fracture generation techniques to aid carbon mineralization.

25 ENERGY STORAGE↗

Investigating Weathering of Basaltic Materials in Gale Crater, Mars: A Combined Laboratory, Modeling and Terrestrial Field Approach

Recent observations from Gale Crater, Mars document past aqueous alteration both in the formation of the Stimson sandstone unit, as well as in the formation of altered fractures within that unit. Geochemical and mineralogical data from Curiosity also suggest Fe-rich amorphous weathering products are present in most samples measured to date. Here we interpret conditions of possible past weathering in Gale Crater using a combination of field, laboratory, and modeling work. In order to better understand secondary Fe-rich phases on Mars, we are examining formation of weathering products in high Fe and Mg and low Al serpentine soils in the Klamath Mountains, CA. We have isolated potential weathering products from these soils, and are analyzing them using synchrotron μXRF and μXRD as well as FullPat for a direct comparison to analyses from Gale Crater. In order to interpret the implications of the persistence of potential secondary Fe-containing phases on Mars, we are also measuring the dissolution rates of the secondary weathering products allophane, Fe-rich allophane, and hisingerite. Ongoing dissolution experiments of these materials suggest that they dissolve significantly more rapidly than more crystalline secondary minerals with similar chemical compositions. Finally, to quantify the specific conditions of past aqueous alteration in Gale Crater we are performing reactive transport modeling of a range of possible past environmental conditions. Specifically, we are testing the conditions under which a Stimson unit-like material forms from a parent material similar to Rocknest or Bagnold eolian deposits, and the conditions under which observed altered fracture zones form from a Stimson unit-like parent material. Our modeling results indicate that the formation of the Stimson unit is consistent with leaching of an eolian deposit with a solution of pH = 6-8, and that formation of the altered fracture zones is consistent with leaching with a very acidic (pH = 2-3) high sulfate solution containing Ca. These results suggest circumneutral pH conditions during authigenesis or early diagenesis in the Stimson formation sediments followed by diagenetic alteration by very acidic solutions along fracture zones.

Hausrath, Elisabeth↗

A Quantitative NMR Analysis of Phosphorus in Carbonaceous and Ordinary Chondrites

Phosphorus is important in a number of biochemical molecules, from DNA to ATP. Early life may have depended on meteorites as a primary source of phosphorus as simple dissolution of crustal apatite may not produce the necessary concentration of phosphate. Phosphorus is found in several mineral phases in meteorites. Apatite and other Ca- and Mg phosphate minerals tend to be the dominant phosphorus reservoir in stony meteorites, whereas in more iron-rich or reduced meteorites, the phosphide minerals schreibersite, (Fe, Ni)3P, and perryite, (Ni, Fe)5(Si, P)2 are dominant. However, in CM chondrites that have experienced significant aqueous alteration, phosphorus has been detected in more exotic molecules. A series of phosphonic acids including methyl-, ethyl-, propyl- and butyl- phosphonic acids were observed by GC-MS in Murchison. Phosphorian sulfides are in Murchison and Murray. NMR spectrometry is capable of detecting multiple substances with one experiment, is non-destructive, and potentially quantitative, as discussed below. Despite these advantages, NMR spectrometry is infrequently applied to meteoritic studies due in large part to a lack of applicability to many compounds and the relatively high limit of detection requirements. Carbon-13 solid-state NMR has been applied to macromolecular carbon in Murchison. P-31 NMR has many advantages over aqueous carbon-13 NMR spectrometry. P-31 is the only isotope of phosphorus, and P-31 gives a signal approximately twice as strong as C-13. These two factors together with the relative abundances of carbon and phosphorus imply that phosphorus should give a signal approximately 20 as strong as carbon in a given sample. A discussion on the preparation of the quantitative standard and NMR studies are presented

Pasek, M. A.↗

Plant Growth Experiments in Zeoponic Substrates: Applications for Advanced Life Support Systems

A zeoponic plant-growth system is defined as the cultivation of plants in artificial soils, which have zeolites as a major component (Allen and Ming, 1995). Zeolites are crystalline, hydrated aluminosilicate minerals that have the ability to exchange constituent cations without major change of the mineral structure. Recently, zeoponic systems developed at the National Aeronautics and Space Administration (NASA) slowly release some (Allen et at., 1995) or all of the essential plant-growth nutrients (Ming et at., 1995). These systems have NH4- and K-exchanged clinoptilolite (a natural zeolite) and either natural or synthetic apatite (a calcium phosphate mineral). For the natural apatite system, Ca and P were made available to the plant by the dissolution of apatite. Potassium and NH4-N were made available by ion-exchange reactions involving Ca(2+) from apatite dissolution and K(+) and NH4(+) on zeolitic exchange sites. In addition to NH4-N, K, Ca, and P, the synthetic apatite system also supplied Mg, S, and other micronutrients during dissolution (Figure 1). The overall objective of this research task is to develop zeoponic substrates wherein all plant growth nutrients are supplied by the plant growth medium for several growth seasons with only the addition of water. The substrate is being developed for plant growth in Advanced Life Support (ALS) testbeds (i.e., BioPLEX) and microgravity plant growth experiments. Zeoponic substrates have been used for plant growth experiments on two Space Shuttle flight experiments (STS-60; STS-63; Morrow et aI., 1995). These substrates may be ideally suited for plant growth experiments on the International Space Station and applications in ALS testbeds. However, there are several issues that need to be resolved before zeoponics will be the choice substrate for plant growth experiments in space. The objective of this paper is to provide an overview on recent research directed toward the refinement of zeoponic plant growth substrates.

Ming, Douglas W.↗

Dynamic Surface Incorporation of Pb 2+ Ions at the Actively Dissolving Calcite (104) Surface

The reaction of dissolved Pb 2+ with calcite surfaces at near-equilibrium conditions involves adsorption of Pb 2+ and precipitation of secondary heteroepitaxial Pb-carbonate minerals. A more complex behavior is observed under far-from-equilibrium conditions, including strong inhibition of calcite dissolution, development of microtopography, and near-surface incorporation of multiple monolayers (ML) of Pb 2+ without precipitation of secondary phases [where 1 ML ≡ 1 Ca/20.2 Å 2 , the crystallographic site density of the calcite (104) lattice plane]. However, the mechanistic controls governing far-from-equilibrium reactivity are not well understood. Here, in this study, we observe the interfacial incorporation of dissolved Pb 2+ during the dissolution of calcite (104) surfaces at pH ~3.7 in a flow-through reaction cell, revealing the formation of a ~1 nm thick Pb-rich calcite layer with a total Pb coverage of ~1.4 ML. These observations of the sorbed Pb distribution used resonant anomalous X-ray reflectivity, X-ray fluorescence, and nanoinfrared atomic force microscopy. We propose that this altered surface layer represents a novel sorption mode that is stabilized by conditions of sustained disequilibrium. This behavior may significantly impact the transport of dissolved metals during disequilibrium processes occurring in acid mine drainage and subsurface CO 2 injection and, if appropriately accounted for, could improve the predictive capability of geochemical reactive-transport models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unraveling Hydrogen Induced Geochemical Reaction Mechanisms through Coupled Geochemical Modeling and Machine Learning

Underground hydrogen storage (UHS) provides a promising large-scale, long-term energy storage solution. A reasonable recovery of stored hydrogen is critical for a successful storage scheme. However, in subsurface reservoirs hydrogen is subject to active geochemical reactions that might result in hydrogen loss. In this study, we implemented a geochemical modeling approach coupled with an unsupervised machine learning technique called non-negative matrix factorization (NMF) to unravel the complex brine-rock-H 2 geochemical processes responsible for hydrogen losses, with particular focus on sulfate reduction reactions. NMF is applied to modeled mineral evolution and fluid component profiles to retrieve profiles that can be interpreted to more easily assess competing processes. NMF decouples simulated competing equilibrium reactions. This facilitates separation of overlapping reaction profiles from redox processes, dissolution fronts, and secondary precipitation while considering the effects of simulation parameters such as salinity, temperature, and total H 2 pressure. NMF successfully discriminates these competing effects in nonlinear ways, allowing robust interpretation. In addition, NMF reveals subtle coupled mineral associations and reaction fronts that are invisible to conventional model analysis. This integrated approach strengthens the conceptual understanding of complex nonlinear hydrogen-brine-rock interactions and advances geochemical research on UHS systems to resolve complexities in modeled geochemical systems without the need for direct experiments or prior knowledge. Furthermore, this study highlights the efficacy of combining geochemical modeling with machine learning techniques to enhance the interpretability of the intricate geochemical simulation output through deciphering the overlapping reaction path that cannot be achieved only using conventional analysis of geochemical models alone.

08 HYDROGEN↗

Carbon mineralization pathways in interfacial adsorbed water nanofilms

Carbon mineralization in humidified carbon dioxide offers a promising route to mitigate anthropogenic emissions in a world stressed by water security. Despite its technological importance, our understanding of carbonation in water-poor environments lags, as traditional dissolution-precipitation pathways struggle to explain the adsorbed water nanofilm-mediated reactivity. Here, we utilize in operando X-ray diffraction (XRD) and advanced molecular simulations to investigate nanoconfined reactions driving forsterite carbonation, the magnesium-rich olivine. By examining magnesium ion dissolution and transport in atomistic simulations of the forsterite-water-carbon dioxide interface and comparing these with the in operando XRD activation energies, we identify both processes as rate-limiting at saturation. Our simulations reveal a mechanistic view of interfacial carbonation, where dissolution and precipitation are mediated by anomalous quasi two-dimensional diffusion. The transport process involves intermittent diffusive hopping in the desorbed state, separated by crawling events that are spatially short but temporally long. This understanding transcends carbon mineralization, with implications for understanding the transport of contaminants in geosystems, the design of multifunctional materials, water desalination, and molecular recognition systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental Constraints on the Origin of Lunar High-Ti Ultramafic Glasses

Phase equilibria and dissolution rate experiments are used to develop a petrogenetic model for the high-Ti lunar ultramafic glasses. Near-liquidus phase relations of the Apollo 14 black glass, the most Ti-rich lunar ultramafic glass, are determined to 2.2-GPa. The liquidus is saturated with Cr-spinel at 1-atm, olivine between approximately 0.5- and 1.5-GPa, and low-Ca pyroxene + Cr-spinel above 1.5-GPa. Ilmenite does not crystallize near the liquidus and implies that high-Ti ultramafic glasses are not produced by melting of an ilmenite-saturated source. We infer that high-Ti ultramafic magmas are derived from low-Ti ultramafic parent magmas by assimilation of ilmenite +/- clinopyroxene +/- urKREEP +/- pigeonite in the shallow lunar interior. Heat is provided by adiabatic ascent of the low-Ti ultramafic primary magmas from the deeper lunar interior and crystallization of olivine during assimilation. The assimilation reaction is modeled by mass balance and requires that ilmenite and high-Ca pyroxene are assimilated in a approximately 3:1 ratio, a much higher ratio than the proportion in which these minerals are thought to exist in the lunar interior. In an effort to understand the kinetic controls on this reaction, the dissolution of ilmenite is examined experimentally in both low- and high-Ti lunar magmas. We find that ilmenite dissolves incongruently to Cr-spinel and a high-Ti melt. The dissolution reaction proceeds by a diffusion-controlled mechanism. An assimilation model for the origin of high-Ti melts is developed that leaves the magma ocean cumulates in their initial stratigraphic positions and obviates source hybridization models that require lunar overturn.

Wagner, T. P.↗

Saponite Dissolution Experiments and Implications for Mars

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

Luu, N. C.↗

Space Resources Roundtable 2

Contents include following: Developing Technologies for Space Resource Utilization - Concept for a Planetary Engineering Research Institute. Results of a Conceptual Systems Analysis of Systems for 200 m Deep Sampling of the Martian Subsurface. The Role of Near-Earth Asteroids in Long-Term Platinum Supply. Core Drilling for Extra-Terrestrial Mining. Recommendations by the "LSP and Manufacturing" Group to the NSF-NASA Workshop on Autonomous Construction and Manufacturing for Space Electrical Power Systems. Plasma Processing of Lunar and Planetary Materials. Percussive Force Magnitude in Permafrost. Summary of the Issues Regarding the Martian Subsurface Explorer. A Costing Strategy for Manufacturing in Orbit Using Extraterrestrial Resources. Mine Planning for Asteroid Orebodies. Organic-based Dissolution of Silicates: A New Approach to Element Extraction from LunarRegohth. Historic Frontier Processes Active in Future Space-based Mineral Extraction. The Near-Earth Space Surveillance (NIESS) Mission: Discovery, Tracking, and Characterization of Asteroids, Comets, and Artificial Satellites with a microsatellite. Privatized Space Resource Property Ownership. The Fabrication of Silicon Solar Cells on the Moon Using In-Situ Resources. A New Strategy for Exploration Technology Development: The Human Exploration and Development of Space (HEDS) Exploratiori/Commercialization Technology Initiative. Space Resources for Space Tourism. Recovery of Volatiles from the Moon and Associated Issues. Preliminary Analysis of a Small Robot for Martian Regolith Excavation. The Registration of Space-based Property. Continuous Processing with Mars Gases. Drilling and Logging in Space; An Oil-Well Perspective. LORPEX for Power Surges: Drilling, Rock Crushing. An End-To-End Near-Earth Asteroid Resource Exploitation Plan. An Engineering and Cost Model for Human Space Settlement Architectures: Focus on Space Hotels and Moon/Mars Exploration. The Development and Realization of a Silicon-60-based Economy in CisLunar Space. Our Lunar Destiny: Creating a Lunar Economy. Cost-Effective Approaches to Lunar Passenger Transportation. Lunar Mineral Resources: Extraction and Application. Space Resources Development - The Link Between Human Exploration and the Long-term Commercialization of Space. Toward a More Comprehensive Evaluation of Space Information. Development of Metal Casting Molds by Sol-Gel Technology Using Planetary Resources. A New Concept in Planetary Exploration: ISRU with Power Bursts. Bold Space Ventures Require Fervent Public Support. Hot-pressed Iron from Lunar Soil. The Lunar Dust Problem: A Possible Remedy. Considerations on Use of Lunar Regolith in Lunar Constructions. Experimental Study on Water Production by Hydrogen Reduction of Lunar Soil Simulant in a Fixed Bed Reactor.

Ignatiev, A.↗

Examining Weathering of Magnesite in an Arid Environment: Implications For Jezero Crater

Introduction:Orbiter data indicatethe presence of carbonates in severallocations on the surface of Mars[1],but Jezero crater, landing site of the Perseverancerover,is the only known location where carbonatesap-pear coincident with evidence of fluvialand lacustrineactivity [2].On Earth, carbonates in close proximity to these paleoenvironments mayindicatethe presence of past microbial life,like stromatolites[3], that could re-sult inbiosignatures [2]. However,in other cases,car-bonates can also form throughthe alteration of mafic materialwiththe introductionof carbonic acid[4].Hy-drated magnesites have also been found in evaporative environments along lake shores, and in playas[5,6,7].Correctly interpreting past carbonates on Mars is there-fore critical in the search for past signs of life. In Jezero crater,both thenorthernand western fans haveMg-rich carbonates intermixed with olivine-rich material[8].According to CRISM data, magnesite(MgCO3), along with hydromagnesite(Mg5(CO3)4(OH)2•4H2O), arepotential candidatesfor these Mg-carbonates [2]. Considering the spatial con-text with olivine,there aremultiplepotential explana-tions for the presence ofMg-carbonatesin this locationincludingin-situformation via alterationof olivine-rich materialwith carbonic acid,transportationfrom farther up in the watershed, or precipitation of lacustrine car-bonates[2]. The formation of hydromagnesite rather than magnesite is favored when Mg2+saturated solutions have a high CO32-/HCO3-ratio, which, on Earth, is thought to be caused byinflow of groundwater [4]. Additionally, Mg-carbonates tend to precipitate under high pH condi-tions and are unstable at lower pH conditions [5]. Hy-dromagnesite is stable at atmospheric CO2pressure and temperature conditions common to most Earth surface environments [9]. However, it is subject to transfor-mation to magnesite after dehydration and concomitant brucite formation or dissolution and reprecipitation [10].Previousresearch suggests that hydrated car-bonates, including hydromagnesite, can formas weath-ering productsof mafic minerals in the presenceof H2O and CO2in subfreezing temperatures and would not de-hydrate under Martian atmospheric conditions [11,12].It is critical to understand the formation conditions of Mg-carbonatesbecause of the different implications for the past history of Martian environments. Therefore, in this work we are investigating the weathering of Mg-carbonatesin arid environments to helpbetter understand Mg-carbonates in Jezero crater. Study Area:The Ala-Mar Mines(East and West)near Ely, NVare the site ofmultiple magnesitedepositsfound within a calcareous tuff formationthat overlies Tertiary aged volcanic rocks.Here,magnesiteis formed via the alteration of the calcareous tuff and occurs innodules, veins,and lenses[13]. Previous work suggests magnesite deposits are associated with faults [13]. Within the West Mine, magnesite can be found in two maincontexts: (1) relatively circular zones of cauli-flower-like material found within (2) a more massivelensthat is heavily fractured on the surface.Methods.Samplesof both the cauliflower texture and more massive materialwere collectedat Ala Mar West Mine. Both samples were thenpowdered, sieved and analyzed with an inXitu Terra Portable XRD. The program QualX was used to identify potential mineral phases [14].Both samples were also optically inspected using 10x and 20x hand lenses.Figure 1. XRD patterns for the cauliflower magnesite (top) and massive magnesite (bottom). Ongoing and future work on the samples discussed above includes scanning electron microscopy (SEM), electron microprobe analysis (EMPA), and near-infra-red spectroscopy to determine whether hydromagnesite is present. Separation and analysis of the clay-size frac-tionby XRD will helpto better identify any phyllosili-cate phases present. Results and Discussion:Both textures are a white to light tan with a porcelain luster on weathered sur-faces, along with minor iron staining in some areas. Likewise, both textures are white with a porcelain luster on fresh surfaces. When broken apart, the massive mag-nesite shows macroscopic crystals, unlike the cauli-flower magnesite. XRD analysis shows that both samples have high concentrationsof magnesite with lesser amounts of thecarbonatemineral huntite(Mg3Ca(CO3)4; Figure1).The more massive samplecontainsa serpentine-groupmineral,with lizardite being apotential candidate. The cauliflower sample has several minor peaks that may correspond to hydromagnesite(Figure 1), although more work is needed to confirm this.Additionally, thecauliflower deposits closely resemble hydromagnesite deposits found in southwestern Turkey, formed via mi-crobialites[15].As such, it is likely that moreaqueous alterationor weatheringis occurring at the locations where the cauliflower magnesite is present. However, additional field work will need to be conducted to con-firm this hypothesis. Conclusions and Future Work:Future work will include field mapping of fault locations andadditional samplingof the different magnesite types as well as of the calcareous tuffmaterial.We will also look specifi-cally for potential weathering products of magnesite in this arid location, which may yield important insight into the Mg-carbonates located in Jezero crater. XRD analyses on aPANalytical XRDusing non-ambient stages will be used to investigate the stability of hydro-magnesiteat different humiditiesand temperatures, which has implications for samples to bereturned to Earth in the future. Additionally, thermal and evolved gas analysis of magnesite and hydromagnesite will be compared to results from Gale Craterto help interpret the mineralogy inthat location[16]. The results of this research will further ourunderstanding of carbonate for-mationin volcanic settingsandtheirweathering pro-cessesin arid environments. Acknowledgments:We acknowledge funding for this research from Jacobs Technology at the Johnson Space Center.We would also like to thank Ngoc Luu, Christopher Adcock, Richard Allanson, and the rest of the UNLV Soil Science Teamfor their continued sup-portwith troubleshooting and otherlab work. References:[1] Ehlmann, B.L., and Edwards, C.S. (2014) Annual Review of Earth and Planetary Sci., 42, 291–315. [2] Horgan, B.H.N., et al. (2020) Icarus, 339, 113526. [3] Bosak, T., et al. (2013) Annual Review of Earth and Planetary Sci, 41, 21–44. [4] Pohl, W.L. (1989) Gebriider Borntraege, 28, 1-13. [5] Müller, G., et al. (1972) Die Naturwissenschaften, 59, 158–164. [6] Walter, M.R., et al. (1973) Journal of Sedimentary Pe-trology, 43, 1021–1030. [7] Braithwaite, C.J.R., and Zedef, V. (1994) Sedimentary Geology, 92, 1–5. [8] Goudge, T.A., et al. (2015) JGR: Planets, 120, 775–808. [9] Langmuir, D. (1965) Journal of Geology, 73, 730–754. [10] Zhang, P., et al. (2000) Applied Geo-chem., 286, 1748–1753. [11] Calvin, W.M., et al. (1994) JGR, 99, 14659-14675. [12]Russell, M.J., et al. (1999) Journal of the Geological Society of London, v. 156, p. 869–888. [13] Faust, G.T., and Callaghan, E. (1948) GSA Bulletin, 59, 11–74. [14] Altomare, A., et al. (2015) J. of Applied Crystallography, 48, 598–603. [15] Zedef, V.,et al. (2000) Economic Geology, 95, 429–445. [16] Leshin, L.A. et al., (2013) Science, 341, 1–9

A W Provow↗

Effects of Interactions Between Produced Formation Fluid and Rock Matrix on Pore Structure of Caney Shale, Southern Oklahoma

ABSTRACT: Rock-fluid interactions change properties of shales during exploitation. To investigate effects of rock-fluid interactions on pore structure of shales matrix after hydraulic fracturing, powder samples from two late Mississippian Caney Shale cores in the Ardmore Basin, southern Oklahoma, were used to react with formation produced fluid from the field in the batch reactor analysis. X-ray diffraction for mineralogy and Low-pressure nitrogen adsorption isotherms for pore structure were measured for original, after-7days, and after-30days samples. Results show that the samples consist mainly of quartz, followed by clay minerals, carbonates, and feldspar. The pore sizes of micropore (<2 nm) and mesopore (2-50 nm) increase 14%-233% due to dissolution of pyrite, feldspar, and carbonates after 7 days. Due to the transformation from smectite to illite and the increase of pore size, the specific surface area (SSA) decreases after 7-days interactions. After 30-days interactions, the micropore volume slightly increases and the mesopore and macropore volume decreases. Due to the decrease of pore size, the SSA of 30-days reacted samples increases correspondingly and is lower (for the clay-rich sample) or higher (for the calcareous sample) than that of the unreacted samples. Findings improve our understanding of dynamic alteration of shale properties during production. 1. INTRODUCTION Energy demand will continuously grow owing to the increasing global population as well as energy consumption (EIA, 2023). On the other hand, shale gas and oil reshaped the energy market in the United States, enabling the United States to become a net-export of natural gas country in 2017 (EIA, 2023). However, shale reservoirs are challenging tight formations that are still poorly understood in the extraction and production of hydrocarbons (Ross and Bustin, 2009; Curtis et al., 2012; Xiong et al., 2015, 2021a; Li Y. et al., 2016; Gong et al., 2019a; Benge et al., 2021; Awejori et al., 2022; Huang et al., 2022). One of the most challenging topics is the rock-fluid interactions post hydraulic fracturing and its subsequent impacts on the pore structures of fractured formation matrix.

Xiong, Fengyang↗

Experimental Studies of Brines and Evaporites as Applied to Mars: Initial Results from 1998-1999 Runs

We are performing laboratory experiments to determine the concentrations and rates of dissolution of ions that could occur in closed, juvenile groundwater systems on Mars. Our approach is to incubate unaltered Mars-analog minerals in initially pure liquid water in contact with a Mars gas mixture for one year. At exponentially increasing time intervals, aliquots of the solutions at three different temperatures are extracted and analyzed using standard terrestrial laboratory geochemical techniques. Ultimately, our experiments will produce Mars analog brines which will be freeze dried to create evaporites. The physical and chemical properties of these evaporites will be compared with spacecraft remote sensing and in situ compositional and physical data. Additional information is contained in the original extended abstract.

Moore, J. M.↗

A non-catastrophist explanation for the iridium anomaly at the Cretaceous/Tertiary boundary

The iridium (Ir) anomaly at the Cretaceous/Tertiary (C/T) boundary can be explained by dissolution of normal pelagic limestones producing an insoluble clay residue containing Ir-rich meteoritic material. Further concentration of Ir and other trace metals in the clay can be explained by deposition under reducing conditions. Clay-mineral analyses indicate that the boundary clay is similar to locally derived clays in the limestones above and below the boundary, and contains no detectable exotic components. This supports a terrestrial origin for the boundary clay. The genesis of the boundary clay is attributed to changes in ocean chemistry (pH and oxygenation), leading to an interval of widespread dissolution of carbonate sequences in the oceans, and culminating in the development of submarine pyritic hardgrounds and a disconformity of global extent.

Rampino, M. R.↗

Geochemical-hydromechanical couplings during water-serpentinized harzburgite interactions at 20° C and 30 bars

Interaction of groundwater with the serpentinized harzburgites of the upper mantle plays an important role in the geologic carbon cycle and serpentinization processes. Here, in this study, an intact serpentinized harzburgite with more than 60% lizardite from the Semail ophiolite in Oman was reacted with water at near neutral pH and low PCO 2 to observe its dissolution behavior and reaction path within the CaO-MgO-SiO 2 -CO 2 -H 2 O system at 20 °C and 30 bars. In the experiment, mass (i.e. H 2 O, ions) transfer is by diffusion and the selected temperature and pressure conditions mimic water-rock interactions at the shallow portions of most ultramafic rock hosted aquifers. Equilibrium activity-activity diagrams and thermodynamic data were used to compare the experimentally determined reaction path with the theoretical stability boundaries for minerals involved to investigate the evolution of bulk chemical composition, mineralogy, and water composition. The experiments demonstrated that (i) the water-rock interactions increased the pH of the aqueous phase from 5.9 to 7.5 over a period of 18 weeks; (ii) the dissolution of lizardite, orthopyroxene (enstatite), and clinopyroxene (diopside and augite) increased the concentration of Mg, Ca, and Si in the aqueous phase; (iii) the dissolution was incongruent with respect to Mg and Si, favoring Si release at pH > 6 due to (a) breaking of more reactive cation‑oxygen bonds that is consistent with the stoichiometry of magnesium for proton exchange reaction which favors a surface that is enriched in Mg at basic conditions, and (b) preferential dissolution of clinopyroxene Mg 1.30 Ca 0.52 Fe 0.06 Si 2 O 6 ; (iv) the aqueous phase was undersaturated with respect to carbonate (e.g. calcite, magnesite, and hydromagnesite) and hydrous (e.g. lizardite, chrysotile, brucite, and talc) minerals; (v) the bulk chemical composition and mineralogy of the intact serpentinized harzburgite matrix did not change; (vi) the thermodynamic data can successfully predict water-intact serpentinized harzburgite behavior if the water chemical composition can be constrained; and (vii) no detectable macroscopic form of damage (e.g. microcracks forming as a result of differential stress fields due to changes in volume during chemical reaction) was observed.

Carbonation↗

Linking Home Plate and Algonquin Class Rocks through Microtextural Analysis: Evidence for Hydrovolcanism in the Inner Basin of Columbia Hills, Gusev Crater

Examining the his-tory of a rock as the summed history of its constituent grains is a proven and powerful strategy that has been used on Earth to maximize the information that can be gleaned from limited samples. Grain size, sorting, roundness, and texture can be observed at the handlens scale, and may reveal clues to transport regime (e.g. fluvial, glacial, eolian) and transport distance. Diagenetic minerals may be of a form and textural context to allow identification, and to point to dominant diagenetic processes (e.g. evaporitic concentration, intermittent dissolution, early vs. late diagenetic emplacement). Handlens scale features of volcaniclastic particles may be diagnostic of primary vs recycled (by surface processes) grains and may provide information about eruptive patterns and processes. When the study site is truly remote, such as Mars, and when there are severe limitations on sample return or sample analysis with other methods, examination at the hand lens scale becomes critical both for extracting a maximum of information, and for best utilizing finite analytical capabilities.

Mittlefehldt, David W.↗