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At least 253 records · Page 14

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.↗

Micromundos biominerales en las algas rojas

Coralline algae (rhodophyta) populate vast pinkish colour regions of the coast. If you step on them in your bare feet, they might hurt you, because they are hard and sharp. Many organisms find shelter and develop within their tiny branches. Photosynthesis of coralline algae conducts the formation of carbonates that exhibit a fascinating architecture. The alga and its associated microorganisms (microbiota) participate in the formation of these minerals, that accumulate and cement the materials that ultimately shape beaches and coastal lines. Carbonates are susceptible to acid-base chemistry; thus, their structural stability and their dissolution depend on the pH of the surrounding environment. Therefore, these biominerals and the marine organisms that build them (such as algae, corals, mollusks or equinoderms) are vulnerable to ocean acidification. By trying to see beyond our eyesight, we were able to understand that algal branches hide an amazing structural strength, where its microstructure and chemistry play a major role. We found minerals with a vast structural and thermal stability in the algal body, named algal thallus. Currently, basic science explores coralline red and green algae as interesting models to understand carbon sequestration in stable structures. Therefore, this research might inspire the development of technologies to mitigate climate change.

59 BASIC BIOLOGICAL SCIENCES↗

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.↗

Computational and Experimental Investigation of Thermal-Mechanical- Chemical Mechanisms of High-burnup Spent Nuclear Fuel (SNF) Processes at Elevated Temperatures and Degradation Behavior in Geologic Repositories

The overarching goal of the combined computational and experimental R&D activities proposed in this project is to enhance understanding of the mechanisms and thermal-mechanical-chemical (TMC) parameters controlling the instant release fraction (IRF) and matrix dissolution of high-burnup (HB; burnup) spent nuclear fuels (SNFs) and the subsequent formation, stability, and phase transformations of SNF alteration products under long-term storage and geological disposal conditions. Uranium dioxide may undergo oxidative corrosion/alteration, and the IRF may be increased for HB SNF, both of which may affect environmental systems associated with SNF long-term storage and disposal. The oxidative matrix dissolution may form various complex uranyl-based phases, including a rich variety of oxides, silicates, carbonates and other secondary minerals in varied geological environments (e.g., studtite, metastudtite, amorphous uranyl peroxide, uranium trioxide, triuranium octoxide, schoepite, dehydrated schoepite, metaschoepite, becquerelite, soddyite, rutherfordine,...). These uranyl phases generally have higher mobility UO 2 +2 species than less soluble U 4+ phases. However, limited information on the thermodynamic properties and formation kinetics of these uranyl-bearing phases is available to predict explicitly paragenesis under the conditions relevant to long-term storage or disposal. The proposed project draws on complementary expertise and research backgrounds from the team members: (i) to apply a combined ab initio modeling (UNLV/UTEP and SNL) and experimental (UNLV) strategy investigating the high-temperature TMC mechanisms of alteration of SNF under α-radiolysis conditions; (ii) to investigate the mechanistic of phase transformations in UNF degradation products under various conditions expected in long-term storage systems (e.g. (UO 2 )O 2 (H 2 O) 4 → (UO 2 )O 2 (H 2 O) 2 → U 2 O 7 → UO 3 → U 3 O 8 ); (iii) to determine high-accuracy TMC parameters for complex uranyl-based phases formed in storage or geological disposal environments (e.g. UO 3 (H 2 O) 2 , Ca[(UO 2 ) 6 O 4 (OH) 8 ] 8 H 2 O, (UO 2 ) 2 (SiO 4 ) 3 2H 2 O,…). The unforeseen COVID-19 pandemic led to the laboratory/campus closure since March 2020, that resulted in a significant delay in reaching milestones in a satisfactory manner, due to (i) the statewide recommendation from stop-working to later limited work in the lab and work-from-home (WFH), (ii) no in-person interactions, and (iii) a hiring freeze at UNLV. Therefore, a no cost extension (10/01/2021- 9/30/2022) was requested to help make up the time we lost during the global pandemic in 2020-2021, leading to paradigm shifts in the focus of the project in the following three main tasks: Task 1 (Computational), Task 2 (Experimental), and Task 3 (Final report, due on 12/29/2022).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

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↗

Radiocarbon analysis as a method for verifying atmospheric CO 2 uptake during carbon mineralization

Sequestration of atmospheric CO 2 is required to constrain the warming of Earth’s climate. Carbon mineralization refers to the precipitation of carbonate minerals by reaction of CO 2 and Mg- and Ca-rich rocks; if the source of the CO 2 is atmospheric and the precipitated carbonate is protected from subsequent dissolution, this process at sufficient scale may be able to reliably draw down atmospheric greenhouse gas levels. Such reactions occur passively in ultramafic settings and previous work has demonstrated that they actively draw down local CO 2 (g) concentrations. However, a method for unambiguously attributing the sequestered carbon solid product to atmospheric sources is still lacking. Here, we test if radiocarbon can be used to verify that the carbon being incorporated into carbonate minerals during carbon mineralization is atmospheric in origin. Additionally, samples from recently exposed ultramafic sites are analyzed and the results demonstrate the utility of this technique for verifying true atmospheric carbon reduction.

58 GEOSCIENCES↗

Selective sulfur removal from semi-dry flue gas desulfurization coal fly ash for concrete and carbon dioxide capture applications

High-sulfur mixed fly ash residues from semi-dry flue gas desulfurization units in coal-fired power plants are unsuitable for use as supplementary cementitious material (SCM) for concrete production or carbon dioxide utilization. In this work, we explore the potential for upcycling a representative spray dry absorber ash (10.44 wt% SO 3 ) into concrete-SCM by selective sulfur removal via weak acid dissolution while simultaneously exploring the possibility for CO 2 capture. Towards this effort, parametric studies varying liquid-to-solid ratio, acidity, and CO 2 pressure were conducted in a batch reactor to establish the sulfur removal characteristics in de-ionized water, nitric acid, and carbonic acid, respectively. The dissolution studies show that the leaching of sulfur from calcium sulfite hemihydrate, which is the predominant S phase, is rapid and achieves a concentration plateau within 5 min, and subsequently, appears to be controlled by the primary mineral solubility. Here, preferential S removal was sufficient to meet SCM standards (e.g., 5.0 wt% as per ASTM C618) using all three washing solutions with 0.62–0.72 selectivity (S^), defined as the molar ratio of S to Ca in the leachate, for a raw fly ash with bulk S^ = 0.3. Acid dissolution with 1.43 meq/g of ash or under 5 atm CO 2 retained > 18 wt% CaO and other Si-, Al-rich phases in the fly ash. Based on the experimental findings, two sulfur removal schemes were suggested for either integration with CO 2 capture and utilization processes using flue gas or to produce fly ash for use as a SCM.

01 COAL, LIGNITE, AND PEAT↗

Emergent Behavior at the Calcite–Water Interface during Reactive Transport in a Simple Microfluidic Channel

Geochemical reactive transport processes in natural mineral-fluid systems may produce a wide array of emergent phenomena that are difficult to predict from basic principles and to reproduce in model systems. In this study, we present experimental results obtained from a simple microfluidic system with which we explored the consequences of reacting the calcite (104) cleavage surface with an acidic Pb-bearing solution (pH = 3.5, [Pb] total = 5 mM) as a function of flow rate. This system is relevant to passive remediation systems for Pb-rich acid mine drainage. We observed periodic banding in the amounts of Pb sorption at flow velocities ≥ 926 μm s -1 , where the band spacing was spatially correlated with the amount of calcite dissolution and the development of micropyramidal topography on the calcite (104) surface. The equivalent coverage of Pb deposited in these Pb-rich bands was at least several monolayers per unit cell, yet there was no evidence for precipitation of any secondary Pb phase implying incorporation of Pb within the near-surface calcite lattice. We also observed spatial variations in nucleation and growth of euhedral secondary Pb-carbonate minerals hydrocerusite and cerussite at flow rates ≤ 278 μm s -1 ,. These findings demonstrate potential for exploiting the rich phenomenology afforded by the interplay among transport phenomena and chemical kinetics in experimental systems designed to yield deeper insights into geochemical self-organization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

In-situ thermodynamics measurements at metal oxides-solution interfaces using Flow Adsorption Microcalorimetry.

Mineral-fluid interfaces are the principal sites of geochemical processes near Earth’s surface, hosting chemical reactions that play a fundamental role in (bio)geochemical cycles and in the fate and transport of anthropogenic contaminants, and that effectively control the compositions of soil and water environments. These complex interfaces are critical for our energy and environmental future. The mineral-fluid interface has been studied in an unprecedented level of detail with both experimental and computational approaches, separately and in combination. However, conspicuously missing from studies of the mineral-fluid interface are direct measurements of the energies of ion sorption and exchange. The literature on energetics and enthalpies of exchange, adsorption, dissolution, precipitation, and surface protonation reactions, especially those directly supported by experimental data, remains scarce despite their fundamental nature. The overarching goal of this project is to complete a systematic study of the thermodynamics properties of interfacial reactions at four MO surfaces (Rutile (α-TiO2), Quartz (SiO2), boehmite (γ-AlOOH) and goethite (α-FeOOH)) through the application and construction of novel flow adsorption microcalorimetry techniques and instrumentations. These unique and specialized microcalorimeters will operate at various temperatures and solution chemical compositions allowing for in-situ measurements across metal oxides and ligands of various characteristics. The overall research goal will be accomplished by completing the following three specific objectives (O): O1) Determine the energetics of surface protonation and deprotonation, ion exchange and ligand sorption reactions; O2) Investigate the surface charge thermodynamic properties under a range of temperature and solution chemical compositions; and O3) Develop predictive trends of the interplay between MO structure, surface coverage and surface reactivity. In addition to key thermodynamics parameters, calorimetric measurements provide a wealth of mechanistic information about reactions energetics and kinetics, surface charge characteristics, and structure-reactivity or selectivity relationships, all obtained in-situ and in real-time. This report includes science highlights from various projects completed over the performance period of the project. Also listed are dissemination opportunities, people supported on the grant and the impact on available physical resources and the discipline as a whole.

58 GEOSCIENCES↗

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.↗

Understanding the Importance of Labile Fe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron Oxyhydroxides

Transformation of metastable Fe(III) oxyhydroxides is a prominent process in natural environments and can be significantly accelerated by the coexisting aqueous Fe(II) (Fe(II) aq ). Recent evidence points to the solution mass transfer of labile Fe(III) (Fe(III) labile ) as the primary intermediate species of general importance. However, a mechanistic aspect that remains unclear is the dependence of phase outcomes on the identity of the metastable Fe(III) oxyhydroxide precursor. Here, we compared the coupled evolution of Fe(II) species, solid phases, and Fe(III) labile throughout the Fe(II)-catalyzed transformation of lepidocrocite (Lp) versus ferrihydrite (Fh) at equal Fe(III) mass loadings with 0.2–1.0 mM Fe(II) aq at pH = 7.0. Similar to Fh, the conversion of Lp to product phases occurs by a dissolution–reprecipitation mechanism mediated by Fe(III) labile that seeds the nucleation of products. Though for Fh we observed a transformation to goethite (Gt), accompanied by the transient emergence and decline of Lp, for initial Lp we observed magnetite (Mt) as the main product. Further, a linear correlation between the formation rate of Mt and the effective supersaturation in terms of Fe(III) labile concentration shows that Fe(II)-induced transformation of Lp into Mt is governed by the classical nucleation theory. When Lp is replaced by equimolar Gt, Mt formation is suppressed by opening a lower barrier pathway to Gt by heterogeneous nucleation and growth on the added Gt seeds. The collective findings add to the mechanistic understanding of factors governing phase selections that impact iron bioavailability, system redox potential, and the fate and transport of coupled elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimentally simulated sea level rise destabilizes carbon-mineral associations in temperate tidal marsh soil

How sea level rise (SLR) alters carbon (C) dynamics in tidal salt marsh soils is unresolved. Changes in hydrodynamics could influence organo-mineral associations, influencing dissolved organic carbon (DOC) fluxes. As SLR increases the duration of inundation, we hypothesize that lateral DOC export will increase due to reductive dissolution of C-bearing iron (Fe) oxides, destabilizing soil C stocks and influencing greenhouse gas emissions. To test this, soil cores (0–8 cm depth) were collected from the high marsh of a temperate salt marsh that currently experiences changes in water level and soil redox oscillation due to spring-neap tides. Mesocosms experimentally simulated SLR by continuously inundating high marsh soils and were compared to mesocosms with Control conditions, where the water level oscillated on a spring-neap cycle. Porewater DOC, lateral DOC, and porewater reduced Fe (Fe 2+ ) concentrations were significantly higher in SLR treatments (1.7 ± 0.5 mM, 0.63 ± 0.14 mM, and 0.15 ± 0.11 mM, respectively) than Control treatments (1.2 ± 0.35 mM, 0.56 ± 0.15 mM, and 0.08 ± 01 mM, respectively Solid phase analysis with Fe extended X-ray absorption fine-structure spectroscopy further revealed that SLR led to > 3 times less Fe oxide-C coprecipitates than Control conditions In addition, the overall global warming potential (GWP) decreased under SLR due to suppressed CO 2 emissions. Our data suggest that SLR may increase lateral C export of current C stocks by dissolving C-bearing Fe oxides but decrease the overall GWP from emissions of soil trace gases. Finally, these findings have implications for understanding the fate of SOC dynamics under future SLR scenarios.

dissolved organic carbon↗