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Data Processing for the Near Earth Asteroid Rendezvous (NEAR), X-ray and Gamma-ray Spectrometer (XGRS) Ground System

An X-ray and Gamma-ray spectrometer (XGRS) is onboard the Near Earth Asteroid Rendezvous (NEAR) spacecraft to determine the elemental composition of the surface of the asteroid 433Eros. The Eros asteroid is highly non-spherical in physical shape and the development of data management and analysis methodologies are in several areas a divergence from traditional remotely sensed geographical information systems techniques. Field of view and asteroid surface geometry must be derived virtually and then combined with real measurements of solar, spectral and instrument calibration information to derive meaningful scientific results. Spatial resolution of planned geochemical maps will be improved from the initial conditions of low statistical significance per integration by repeated surface flyovers and regional spectral accumulation. This paper describes the results of a collaborative effort of design and development of the NEAR XGRS instrument ground system undertaken by participants at the Goddard Space Flight Center, University of Arizona, Cornell University, Applied Physics Laboratory, and Max Plank institute.

McClanahan, Timothy P.↗

Data Processing for the Near Earth Asteroid Rendezvous (NEAR), X-Ray and Gamma-Ray Spectrometer (XRS) Ground System

An X-ray and Gamma-ray spectrometer (XGRS) is onboard the Near Earth Asteroid Rendezvous (NEAR) spacecraft to determine the elemental composition of the surface of the asteroid 433Eros. The Eros asteroid is highly non-spherical in physical shape and the development of data management and analysis methodologies are in several areas a divergence from traditional remotely sensed geographical information systems techniques. Field of view and asteroid surface geometry must be derived virtually and then combined with real measurements of solar, spectral and instrument calibration information to derive meaningful scientific results. Spatial resolution of planned geochemical maps will be improved from the initial conditions of low statistical significance per integration by repeated surface flyovers and regional spectral accumulation. This paper describes the results of a collaborative effort of design and development of the NEAR XGRS instrument ground system undertaken by participants at the Goddard Space Flight Center, University of Arizona, Cornell University, Applied Physics Laboratory, and Max Plank institute.

McClanahan, Timothy P.↗

Lunar and Planetary Science XXXV: Lunar Remote Sensing: Fire, Ice, and Regolith

The session "Lunar Remote Sensing: Fire, Ice, and Regolith" included the following:Compositional and Structural Study of the Aristarchus Plateau from Integrated UV-VIS-NIR Spectral Data; Clementine 2.7-?m Data: Mapping the Mare and Searching for Water; On the Search for Water at the Lunar Poles: Results of Forward Modeling of Permanently Shaded Areas and Lunar Prospector Measurements; Searching the Moon for Aluminous Mare Basalts Using Compositional Remote-Sensing Constraints I: Finding the Regions of Interest; Semi-automated Extraction of Contours from Lunar Topographic Maps; Basalts in Mare Humorum and S.E. Procellarum; The Hansteen and Helmet Volcanic Dome Regions on the Moon: Stratigraphy and Ages; Derivation of Elemental Abundance Maps at 15-km Spatial Resolution from the Merging of Clementine Optical and Lunar Prospector Geochemical Data; Remote Sensing and Geologic Studies of the Balmer Region of the Moon; Lava Flows in Mare Nubium and Mare Cognitum: A Geological History Based on Analysis of Multispectral Data; Development of Ground-based Lunar VIS/NEAR IR Spectral Imager; A BRDF Measurement Apparatus for Lab-based Samples; A New Source of High Resolution Lunar Images: Amateur Astronomers! ; Leakage of Gamma Rays and Neutrons from Thick Targets Bombarded by Energetic Protons; Progress on Reviving Lunar Orbiter: Scanning, Archiving, and Cartographic Processing at USGS; Modeling Lateral and Vertical Mixing by Impact Cratering with Applications for the Moon; Optical Maturity Study of Stuart#s Crater Candidate Impact; Evidence for Three Basins Beneath Oceanus Procellarum; and Ellipses of the South Pole-Aitken Basin: Implications for Basin Formation.

Source record↗

Cold and Cryogenic Curation of Lunar Volatile Samples Returned to Earth

The study of volatile compounds and volatile elements, such as H, He, C, N, O, H2O, CH4, SO2, CO, CO2, NH3, HCN, etc., are commonly used for constraining evolutionary processes on planets, satellites, and asteroids, as well as formulating models of solar system formation. For Lunar science, the recent evidence of regolith and rocks containing small amounts of OH- and/or H2O has renewed scientific interest into the study of lunar volatiles [1, 2]. Future lunar sample return missions will include the study of volatiles as a high priority. Comet particles from the Stardust mission, asteroid particles from Hayabusa, meteorites, and subsurface lunar samples all occupied subfreezing environments prior to collection. Valuable geochemical information on volatiles is often lost when these samples are allowed to reach ambient temperatures on Earth. The ability to store, document, subdivide, and transport extraterrestrial geologic samples while maintaining below freezing or cryogenic temperatures is required for the complete scientific study of such samples, as well as future samples from a wide range of solar system bodies.

Calaway, M. J.↗

Two mechanisms for the spontaneous emergence, execution, and reprogramming of chemical logic circuits

A key question in origin-of-life research is how primitive life or life-like systems obtained reusable and reprogrammable machinery of processing information to respond to various environmental and internal stimuli. One strategy to approach this question is to view living systems as universal chemical computers. This approach focuses upon uncovering how reusable and reprogrammable chemical NOT, AND, and OR logic gates could appear under prebiotically possible scenarios where simple chemicals and second- or lower-order reactions are more frequent than macromolecules and higher-order reactions. In this article, we theoretically model two generic mechanisms of forming Boolean gates based on geochemically plausible reaction systems that could have preceded complex biopolymers. The mechanisms exploit simple bistable autocatalytic systems to encode binary variables and use heterogeneous dilution rates to differentially activate or deactivate autocatalysis in different reactors. We found that NOT, AND, and OR gates, as well as more complex logic circuits, can spontaneously arise from connected, well-mixed flow reactors based on (i) catalysis by a heterodimer between mutually inhibitory autocatalysts or (ii) selectively permeable tunnels connecting reactors. Our results suggest that simple machinery can support the prebiotic emergence of complex chemical logic circuits and provide new guides for experimentally actualizing chemical computation.

Zhen Peng↗

Rapid and automated separation of uranium ore concentrates for trace element analysis by inductively coupled plasma – optical emission spectroscopy/triple quadrupole mass spectrometry

The present study documents an automated approach to performing elemental analysis on a large group uranium ore concentrate (UOC) samples. In this work, 17 UOC samples, 2 quality control samples, and 26 process blanks were purified sequentially through a single 500 μL Uranium and TEtra Valent Actinides (UTEVA®) column. For each sample, the trace elemental impurities were separated from its dissolved uranium matrix on the UTEVA column and collected for analysis by inductively coupled plasma – optical emission spectroscopy / triple quadrupole mass spectrometry (ICP-OES/TQMS). The UTEVA column was subsequently regenerated prior to separation of the following sample. The column was efficiently regenerated, for each UOC, even after processing ~50 mg of uranium, cumulatively. The validity of the method was established by determining the trace impurities of two quality control uranium reference samples (CRM 124–1 and CUP-2). The current trace element measurements from the 17 UOC samples were compared to previously reported values from an interlaboratory comparison exercise, when available. The methodology employed here produces trace elemental analysis with excellent correlation to the previously reported data for many of the elements / samples, particularly when viewed through the context of existing geochemical comparisons tools (e.g. chondrite normalized variation plots).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mineralogical, Elemental, and Tomographic Reconnaissance Investigation for CLPS (METRIC): A Proposed Mission to the Lunar South Pole-Aitken Basin

The global Lunar Magma Ocean (LMO) hypothesis is based on analyses of ferroan anorthosites (FAN), magnesian plutonic rocks (Mg-suite), and KREEPy (Potassium - K; Rare Earth Elements - REE; Phosphorous - P) material present at the Apollo landing sites and the assumed global distribution of these lithologies. However, orbital spacecraft data over the last two decades have highlighted that the location of the Apollo missions within and near the Procellarum KREEP Terrane (PKT) is compositionally anomalous and not representative of the entire lunar surface and suggests that Apollo samples provide a biased view of the Moon. Further, meteorites, which originate from random areas on the lunar surface, including those not visited by Apollo, Luna, or Chang’E-5, provide complementary datasets that reveal a more complex lunar formation and evolution than the simple LMO onion skin model. While many recent investigations support and refine the LMO model, other recent studies have questioned whether this mechanism alone is responsible for the primordial differentiation of the Moon. Thus, relating the distinct and asymmetrically distributed geochemical terranes on the Moon, especially KREEP which is a predicted global LMO product, to lunar formation and differentiation remains a fundamental goal of lunar science. The South Pole-Aitken (SPA) impact carved a two-and-a-half thousand-kilometer basin into the Moon’s ancient crust, excavating material from as deep as the upper mantle. Orbital remote sensing of the basin indicates compositions with elevated thorium (Th) contents and unique mineralogies that provide a window into early lunar structure and LMO processes. We propose to land a powerful characterization laboratory at Birkeland crater on the far side of the Moon–where Th-rich SPA ejecta have been re-exposed near the surface–in order to address outstanding questions about the evolution of the Moon.

K M Cannon↗

MR13A-3183: Microbial and Geochemical Characterization of Groundwater: Implications for Underground Hydrogen Storage Leakage

Underground hydrogen storage (UHS) in geological formations is a key element of the clean energy transition as it enables the decarbonization of the transportation and industrial sectors by decoupling hydrogen production and storage. UHS has many benefits, including low cost, much wider availability, large storage capacity, well-established infrastructure, and increased safety because of geological sealing capabilities. However, the impact of hydrogen (H2) biogeochemical interactions in the presence of subsurface microorganisms is largely neglected from UHS perspectives. These interactions might affect the effectiveness of storage and can even cause H2 to leak into the shallow aquifers. Leakage of H2 into groundwater can change the geochemistry and induce several microbial-driven processes. Microorganisms, such as sulfate-reducers, are naturally abundant in groundwater and consume H2 to produce hydrogen sulfide (H2S), which can contaminate the freshwater drinking groundwater and cause damage to infrastructure. Hydrogen leakage can also trigger microbial reactions responsible for metal mobility, which can impact the water quality. However, the kinetics of these reactions and the temporal impact of hydrogen leakage in groundwater are still unknown. Therefore, a time series hydrogen-groundwater interaction experiment was conducted, and the changes in fluid chemistry and headspace gas composition will be analyzed along with DNA sequencing results to understand the extent and kinetics of biogeochemical reactions that occur if hydrogen leaks into groundwater. In the experiments, Ultra High Purity (UHP) hydrogen gas will be injected into glass vials with groundwater samples, for a designated time period. For each glass-sealed vial, 16S rRNA gene sequencing, IC, ICP-MS, and GC-TCD will be performed. The experiments provide insights into plausible impacts of hydrogen leakage into shallow drinking water aquifers.

Clark, Allison [West Virginia University (WVU)]↗

Niche Partitioning of Microbial Communities at an Ancient Vitrified Hillfort: Implications for Vitrified Radioactive Waste Disposal

A pre-Viking era vitrified hillfort, Broborg, provides a habitat analogue for disposed radioactive waste glass and shows strong niche partitioning among the organisms involved in glass alteration. Microbes cannot be eliminated from radioactive waste disposal facilities and the consequences of bio-colonization must be understood. We use Broborg as a model system to inform what microbial processes might influence long-term radioactive waste glass durability by examining anthropogenic glass that has been subjected to bio-colonization for over 1,500 years. Scanning electron microscopy (SEM) images reveal the surficial biofilm structure, and chemical/mineralogy analysis in combination with deoxyribonucleic acid (DNA) sequencing of samples from the vitrified substrate, the adjacent soil, and the general topsoil provide insight into niche partitioning. The ancient glass niche supports a unique microbial community of bacteria, fungi, and protists that manifests the species response to local geochemical and mineralogical conditions. Communities from the geochemical niche associated with the glass are distinct and less diverse than soil communities. The microbiome of the glass and adjacent soil are dominated by lichens, lichen-associated microorganisms, and other epilithic, endolithic, and epigeic organisms. Pseudomonads dominate the prokaryotic communities on the vitrified material, but not the adjacent soil. In contrast, the general topsoil communities are enriched in plant rhizosphere organisms. Taxa associated with vitrification have bio-corrosive properties that could be detrimental to glass durability, including silicate mineral dissolution, extraction of essential elements, secretion of geochemically reactive organic acids, and dissolution induced by improved water retention. However, these stable long-term biofilms also possess a homeostatic function that could limit glass alteration. Overall, this study demonstrates the potential impacts that microbial colonization and niche partitioning can have on glass alteration and subsequent release of radionuclides from a disposal facility for vitrified radioactive waste.

59 BASIC BIOLOGICAL SCIENCES↗

Time scale for the formation of the earth and planets and its role in their geochemical evolution

The initial mass of the solar nebula is discussed. Models of a massive nebula (two solar masses and more) encounter serious difficulties: an effective mechanism of transfer of the momentum from the central part of the nebula outward, capable of leading to formation of the sun and removal of half the mass of the nebula from the solar system has not been found. As a consequence of the instability of these models, their evolution can end with the formation, not a planetary system, but of a binary star. The possibility is demonstrated of obtaining acceptable growth rates for Uranus and Neptune by prolonging the thickening of preplanetary dust in the region of large masses. The important role of large bodies in the process of formation of the planets is noted. The impacts of such bodies, moving in heliocentric orbits, could have imparted considerable additional energy to the forming Moon, which, together with the energy given off by the joining of a small number of large protomoons, could have led to a high initial temperature of the moon.

Safronov, V. S.↗

Impact of carbonation on leaching of constituents from a cementitious waste form for treatment of low activity waste at the DOE Hanford site

Carbonation can be a major aging process during disposal of alkaline cementitious waste forms and can impact constituent leaching by changes in material alkalinity, pore structure, and controlling mineral phases. The effect of carbonation on the leaching of major and trace constituents from Cast Stone, a cementitious waste form developed to treat high salt content low activity waste, was studied through a combination of leaching experiments and reactive transport simulations. Diffusive transport of constituents in the waste form was evaluated using reactive transport modeling of diffusion-controlled leaching test results and a geochemical speciation model derived from pH-dependent leaching. Comparisons between Cast Stone materials aged under nitrogen, air, and 2% carbon dioxide in nitrogen showed that carbonation impacts solubility, physical retention and observed diffusivity of major and trace constituents. Carbonation under 2% CO 2 decreased the diffusion-controlled leaching of chromium by two orders of magnitude. Finally, modeling results suggest that carbonation may also decrease solubility of technetium while changes to microstructure by carbonation increases effective diffusivity of constituents in Cast Stone.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effect of CO 2 Concentration on the Microbial Activity of Orenia metallireducens (Strain Z6) in Surface Inert Materials

Carbon dioxide (CO 2 ) sequestration has garnered widespread attention as a key strategy for mitigating CO 2 emissions and combating the greenhouse effect. However, the mechanisms underlying the interactions between CO 2 , widespread siliceous minerals and biological processes remain unclear. The present study explored the potential impacts of different CO 2 concentrations on microbial activity, environmental conditions and their feedback on the fate of CO 2 . A total of 20 experimental conditions was created, with the variables including different natural and synthetic siliceous minerals (e.g., quartz sand and a type of commercial glass beads), the presence or absence of the iron-reducing microorganism Orenia metallireducens (strain Z6) and varying CO 2 concentrations (0%, 20%, 50%, 100%) in the presence of ferrihydrite and pyruvate. Geochemical, microbial and mineralogical analyses revealed that elevated CO 2 concentrations significantly inhibited microbial Fe(III) reduction and pyruvate metabolism. Interestingly, compared to cultures without mineral amendments or those with glass beads alone, the addition of quartz sand enabled strain Z6 to better withstand the environmental stress caused by elevated CO 2 , promoting pyruvate fermentation and iron reduction. In addition to an increased pH, the formation of siderite, hematite and vivianite was also observed in the bioactive systems. Although both glass beads and quartz sand were primarily composed of silica, differences in the mineral structure, elemental composition and acid neutralization capacity rendered quartz sand more chemically active and unexpectedly led to greater CO 2 sequestration.

CO2 stress↗

Copper and nickel partitioning in iron meteorites

Trace element analyses using proton induced X-ray emission and synchrotron X-ray fluorescence have been made on metal and troilite from nine iron meteorites representing five geochemical groups. Nickel and copper distribution coefficients D (troilite/metal) vary by factors of 600 and 20, respectively, correlate positively with kamacite bandwidth and correlate negatively with bulk nickel content. Meteorites with bulk Ni of less than 10 percent have Cu-enriched troilite while those with Ni greater than 10 percent have Cu-depleted troilite. Since magmatic evolution and partial melting will produce Cu-enriched troilite only, the observation of Cu-depleted troilite in Ni-rich meteorites is evidence for subsolidus reequilibration, a process which reduces D(Cu) by transfer of Cu to exsolving metal. Elemental redistribution may have played an important role in establishing the present chemical trends in iron meteorites.

Sutton, S. R.↗

Pink Spinel in Apollo Impact Melt Rock 68815: Implications for Mg-Suite Magmatism

Introduction: Magnesian rocks from the lunar highlands are collectively termed the Mg-suite. Characterized by high (>60) Mg# (molar 100×Mg/[Mg+Fe]) in mafic phases and calcic plagioclase, these rocks are plutonic to hypabyssal in origin, and include a range of bulk mineralogies such as troctolites, dunites, norites, gabbronorites, and spinel troctolites [1]. These Mg-suite lithologies have distinct trace element concentrations and ratios that differentiate them from other lunar rock types. These rocks are ancient, generally dated to between 4.5 and 4.1 Ga, although it is unknown if this represents the full range of Mg-suite ages [1–2]. Among the Mg-suite lithologies, the spinel troctolites are relatively rare, to date only found in polymict breccias [3]. Spinel troctolites, as their name suggests, consist of calcic plagioclase and forsteritic olivine, with minor amounts of spinel (MgAl2O4), ± pyroxene and cordierite [1,4]. This form of spinel is often called ‘pink’ spinel because of its appearance in thin section under plane polarized light (PPL; Fig. 1), due to minor amounts of Cr. Spinel troctolites are generally plutonic or hypabyssal in origin (subsequently exhumed and incorporated into polymict breccias), or formed through impact processes (e.g., crystalline impact melt) [5]. A spinel-rich lithology has also been found in the Moscoviense region of the Moon via the Moon Mineralogy Mapper (M3) and lacks other mafic phases [6]. Finally, while the Mg-suite sampled thus far consists of plutonic (or hypabyssal) rocks, the question remains if such magmas could have erupted on the surface of the Moon [7]. These magmas have much lower density than mare basalts, but little sample or remote sensing evidence has been found to support the idea that extrusive Mg-suite volcanism occurred [7]. Here, we present a coordinated microanalytical study of spinel-bearing lithic and mineral clasts found in Apollo sample 68815. These data will be used to understand their petrogenesis (magmatic or impact) and modification histories, and to shed light on the existence of volcanic Mg-suite rocks. Sample Description: Apollo sample 68815 is a polymict impact melt breccia containing a variety of lithic and mineral fragments embedded in devitrified impact melt. This sample was chipped off the top of a boulder at Station 8 during the Apollo 16 mission and had an original weight of nearly 1.8 kg. In this study, we investigated two polished thin sections of 68815: 68815,17 and 68815,148, both containing spinel. Methods: The thin sections of 68815 were studied using optical light microscopy (PPL, cross-polarized light, and reflected light) with a Keyence VHX-7100 Digital Microscope. Each section was then X-ray mapped for 13–14 elements using a Cameca SX100 electron probe microanalyzer (EPMA) located in the Kuiper Materials Imaging and Characterization Facility (KMICF) at the University of Arizona. We have obtained geochemical information about the phases (olivine, plagioclase, spinel, pyroxene) in the thin sections also using the EPMA. In addition, we have used ThermoScientific Helios NanoLab 660 Focused-Ion-Beam Scanning-Electron Microscope (FIB-SEM) and a Hitachi S-4800 SEM (both in KMICF) to obtain backscattered electron (BSE) images and energy dispersive Xray spectrometry (EDS) maps of areas of interest. Using a JEOL 7900F SEM at the Astromaterials Research & Exploration Science (ARES) at NASA Johnson Space Center (JSC), we have obtained electron backscatter diffraction (EBSD) maps of the spinel-bearing portions of the thin sections. The EBSD data were collected under beam conditions of 20 kV, and ~90 μA, with step sizes varying from 0.05 to 2 μm. Following EBSD data collection, we processed the data using AZtecCrystal and MTEX, a free MATLAB toolbox. Results: We have found clasts with subophitic textures, that consist of primarily olivine and plagioclase, with minor amounts of pink Mg-Al spinel and pyroxene (Fig. 1). These clasts are up to ~1 mm in length and contain spinels up to 50 μm across. We have additionally identified pink Mg-Al spinels within the impact melt (i.e., not contained in lithic clasts) in both thin sections. In one instance, a single spinel grain is approximately 300 μm across (Fig. 1b, 2). The spinel fragments embedded in impact melt have varying compositions, typically distinct from the compositions of spinels in the lithic clasts. Spinel-Bearing Clasts: Ten lithic clasts with similar textures and mineral compositions were identified between 68815,17 (two clasts) and ,148 (eight clasts). These clasts fall into two groups. The first has skeletal olivine with intergranular plagioclase, with minor amounts of pyroxene and spinel (Fig. 1a, 2c, 2d). The spinel in these clasts are found amid the plagioclase. The second group have an intergranular texture of olivine and plagioclase, again with minor spinel and pyroxene. The second group may contain spinels surrounded by plagioclase, and spinels enclosed in olivine. Spinels located within both clast types range from no apparent Cr zoning, to reverse zoning (Cr-enrichment inward; Fig. 2d), to normal zoning (Cr-enrichment outward). In the clasts thus far investigated with EPMA, plagioclase compositions range from An# (molar 100×Ca/[Ca+Na+K]) 92–96. Olivine Mg# ranged from 77 to 94, while pyroxene had Mg# from 54–84. Spinel in the clasts have Cr# (molar 100×Cr/[Cr+Al]) 2–4 and Mg# 88–91, which is within the range of pristine and plutonic spinel troctolites [8]. Isolated Spinels: These crystals are generally euhedral to subhedral, and can exhibit reverse Cr zoning (Cr enrichment inward) or no apparent Cr zoning. The spinels thus far investigated via EPMA have Cr# 9–14 and Mg# 65–82. The Cr# for these spinels is within the range reported by [8], but have lower Mg#. Future Work: We will continue to process the EBSD data for these lithic and mineral clasts. We will also continue to characterize these clasts using EPMA and SEM. By thoroughly characterizing the various spinels and spinel-bearing clasts, we aim to constrain the petrogenesis of these minerals and rock fragments. Acknowledgments: We thank NASA for the loan of these thin sections. We thank Ken Domanik and Jerry Chang for their support with data collection. Work was supported by a University of Arizona RII Core Facilities Pilot Program grant and start-up funds to JJB. We acknowledge support from NASA’s Planetary Science Research program for analysis performed at JSC. References: [1] Shearer C. K. et al. (2015) Am. Min. 100, 294–325. [2] Borg L. E. et al. (2020) GCA 290, 312–332. [3] Warren P. H. (1993) Am. Min. 78, 360–376. [4] Dymek R. F. et al. (1976) LPS VII, 2335–2378. [5] Treiman et al. (2019) Am. Min. 104, 370–384. [6] Pieters et al. (2011) JGR: Plan. 116:E00G08. [7] Prissel et al. (2016) Icarus 277, 319–329. [8] Prissel et al. (2016) Am. Min. 101, 1624–1635.

spinel↗

Mars Geochemical Instrument (MarGI): An instrument for the analysis of the Martian surface and the search for evidence of life

The Mars Geochemical Instrument, MarGI, was developed to provide a comprehensive analysis of the rocks and surface material on Mars. The instrument combines Differential Thermal Analysis (DTA) with miniature Gas Chromatography-Ion Mobility Spectrometry (GC-IMS) to identify minerals, the presence and state of water, and organic compounds. Miniature pyrolysis ovens are used to both, conduct DTA analysis of soil or crushed rocks samples, and pyrolyze the samples at temperatures up to 1000 degrees C for GC-IMS analysis of the released gases. This combination of analytical processes and techniques, which can characterize the mineralogy of the rocks and soil, and identify and quantify volatiles released during pyrolysis, has applications across a wide range of target sites including comets, planets, asteroids, and moons such as Titan and Europa. The MarGI analytical approach evolved from the Cometary Ice and Dust Experiment (CIDEX) selected to fly on the Comet Rendezvous Asteroid Flyby Mission (CRAF).

Kojiro, Daniel R.↗

Mechanisms of dissolution from gibbsite step edges elucidated by ab initio molecular dynamics with enhanced sampling

Surface reactions underpin our collective understanding of mineral dissolution. This impacts a range of predictive geochemical models (for weathering, the fate and transport of metals) as well as industrial utilization of minerals. Yet atomistic details are rarely known due to the complex mineral/fluid interfacial environment. There is significant need to understand the mechanistic details of dissolution reactions and how they depend on surface morphology and solution conditions. This work utilizes surface pit models in conjunction with changes to solution composition that mimic pH to explore surface detachment of aluminate from gibbsite, which is a primary source of Al in soils and within the industrial processing of aluminum. Ab initio molecular dynamics simulations with enhanced sampling has been used to explore the detailed process of the detachment, the results of which indicate two potential pathways that are differentiated based upon the extent of water hydration. Here, the heights of the energy barriers depend upon the local morphology which influence the number of bridges (quasi-)simultaneously broken (1 or 2) or the Al-O coordination of the neighboring aluminum atoms (5 or 6) at the armchair edge. pH effects are significant, with a nearly 50% reduction in barrier height under alkaline conditions that are relevant to geothermal fluids and Al extraction from minerals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reactive Transport Modeling of Anthropogenic Carbon Mineralization in Stacked Columbia River Basalt Reservoirs

Numerical simulation of CO2 storage in basalts and related reactive lithologies requires modeling complex, coupled hydrologic and chemical processes, including multi-phase flow and transport, partitioning of CO2 into the aqueous phase, and chemical interactions with aqueous fluids and rock minerals. We conducted reactive transport simulations of the Wallula pilot-scale CO2 injection into the flow tops of the Grande Ronde Basalt using our PNNL STOMP-CO2 simulator with the ECKEChem reactive module. Our mineralization simulation of the ~1,000 tons of injected CO2 into the interflow zones was based on the hydrologic transport model we previously developed. For this work, the simulations considered geochemical reactions involving the basalt components, precipitates, formation brine, and injected CO2. In our benchmark case, carbonate minerals precipitated, resulting in ~20% of the CO2 being mineralized in 10 years. Increasing the reaction rate of a single primary mineral phase (clinopyroxene) by an order of magnitude resulted in a carbon mineralization reaction extent of ~90% over the same time interval. Based on these initial sensitivity analysis results, it is clear that a thorough understanding of primary mineral dissolution rates is required for accurately predicting long-term fate and transport of injected CO2 into basalt formations. Our reactive transport numerical simulations will be key components of commercial-scale CO2 storage operation permitting, de-risking, and optimization in mafic and ultramafic reservoirs.

Cao, Ruoshi↗

The Long-Term Evolution of the Atmosphere of Venus: Processes and Feedback Mechanisms

This work reviews the long-term evolution of the atmosphere of Venus, and modulation of its composition by interior/exterior cycling. The formation and evolution of Venus’s atmosphere, leading to contemporary surface conditions, remain hotly debated topics, and involve questions that tie into many disciplines. We explore these various inter-related mechanisms which shaped the evolution of the atmosphere, starting with the volatile sources and sinks. Going from the deep interior to the top of the atmosphere, we describe volcanic out-gassing, surface-atmosphere interactions, and atmosphere escape. Furthermore, we address more complex aspects of the history of Venus, including the role of Late Accretion impacts, how magnetic field generation is tied into long-term evolution, and the implications of geochemical and geodynamical feedback cycles for atmospheric evolution. We highlight plausible end-member evolutionary pathways that Venus could have followed, from accretion to its present-day state, based on modeling and observations. In a first scenario, the planet was desiccated by atmospheric escape during the magma ocean phase. In a second scenario, Venus could have harbored surface liquid water for long periods of time, until its temperate climate was destabilized and it entered a runaway greenhouse phase. In a third scenario, Venus’s inefficient outgassing could have kept water inside the planet, where hy- drogen was trapped in the core and the mantle was oxidized. We discuss existing evidence and future observations/missions required to refine our understanding of the planet’s history and of the complex feedback cycles between the interior, surface, and atmosphere that have been operating in the past, present or future of Venus.

Venus↗