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The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

Plumlee, G. S.↗

Geochemical Insights Into Volcanic and Lithospheric Evolution of Mars

Introduction: The Martian lithosphere plays a pivotal role in volcanic processes, altering surface features, climate shifts, and the planet's early habitability. Crucially, the rigid lithosphere significantly influences Mars' long-term thermal conditions. Studying various geological eons’ volcanic compositions unveils how the lithosphere has evolved, even though understanding the early Noachian volcanic chemistry remains challenging due to weathering and resurfacing. In this study, newly discovered Noachian volcanic terranes[1-2] along with Hesperian and Amazonian volcanic terranes[3] are considered(Figure 1), to infer the evolution of the Martian lithosphere. Figure 1:Mars topographic map derived from MOLA-HRSC data [4] highlights the study regions including the Noachian volcanic terranes, Arabia Terra (AT), Thaumasia Minor (TM), and the Southwest Margin of Icaria Planum (SWIP)[5].Additionally, the Hesperian volcanic terranes such as Syrtis Major (SM), Hesperia Planum (HP), and, the Amazonian volcanic terranes encompass Elysium Mons (EM), Alba Patera (AP), and Olympus Mons (OM) are marked. Methods and Datasets: We use the most recent elemental mass fraction maps derived from gamma spectroscopy data from the Mars Odyssey 2001mission [6]to ascertain the bulk composition of the Martian landscape. Utilizing the updated geochemical provinces dataset of Mars[7], we consider bulk chemistry variations within our study regions. The maps, at a resolution of 50×50, encompass elements like Al, Ca, Fe, Si, K, Th, H2O, Cl, and S, detected through Gamma-Ray Spectroscopy (GRS) with decimeter scale depth sensitivity[6].Additional major and minor elements like Mg, Na, Ti, P, and Mn, using mass balance methods [8]serve as inputs for melting and crystallization simulations. We employ the pMELTS model with FMQ-3to FMQ oxygen fugacity to estimate the Pressure(P)and melting degree(F)in various eons of volcanic terranes. We have also used conventional thermobarometric calculations to determine their formation P-T conditions, using silica activity and olivine-melt Mg-exchange thermometry[9-10]. Results: Chemical Composition of Studied Volcanic Terranes: To assess formation conditions, we have investigated if GRS-measured compositions signify primary igneous processes by evaluating weathering through the Chemical Index of Alteration (CIA), K/Th ratios, and ternary plots for aqueous alteration. Consistent K/Th ratios and low CIA (<50) across volcanic regions suggest minimal large-scale weathering, affirming well-preserved igneous material extending at decimeter depths. In addition, the calculated bulk compositions align with Martian mantle equilibrium, confirming studied volcanic terranes-Arabia Terra, Thaumasia Minor, and SWIP -as primary or less altered compositions, reinforcing their representativeness at a regional GRS scale on Mars. We have also estimated the bulk compositions of Hesperian and Amazonian volcanic terranes shown in Figure 1. All volcanic terranes represent the primary or minimally altered composition. Temporal Evolution of Martian Volcanic Terranes: Our results show P-T conditions ranging from 1.3-1.6 GPa and 1350-1390°C for Noachian terranes, while Hesperian volcanic terranes vary from 1.6-1.7 GPa and 1370-1395°C, and Amazonian volcanic terranes range between 1.9-2.8 GPa and 1380-1415°C. Our analyses correspond to lithospheric thicknesses/ depth of melting for Noachian which ranges from110-135 km, 120-235 km for Hesperian terranes, and 160-235 km for Amazonian terranes. Partial melting percentages (F) range from 8-12% for Noachian, 10-11% for Hesperian, and 10-12% for Amazonian. We have also calculated mantle potential temperatures (Tp) to show variations across epochs(Figure 2). Heat flux estimation shows variations from 51-65 mW/m2 for Noachian, 38-45 mW/m2for Hesperian, and 27-39 mW/m2for Amazonian terranes, implying temporal changes in lithospheric thickness and heat flow. Comparison of Noachian volcanic terranes with Hesperian and Amazonian reveals variations in lithospheric thickness and heat flux, indicating potential implications for Martian surface conditions, including volcanic activity, climate evolution, and early habitability. Figure 2: P-T diagram displays formation conditions of studied Martian volcanic regions using GRS data, alongside Noachian-age surface basalt samples from Gusev, Gale, and Jezero. Dashed lines represent Martian mantle potential temperatures, calculated by adding the latent heat of fusion to the equilibrium temperature at which melt and solid mantle coexist and subtracting the Martian adiabatic gradient corresponding to the depth of melt. The solid line shows the Martian mantle solidus [11].Discussion& Implication: The study explores Martian volcanic activity across eons. Uniform lithospheric thickness from the Noachian to Hesperian eons suggests persistent weak plumes until Hesperian, influencing heat flow variations. Noachian's high heat flux, likely due to concentrated radioactive elements, shows spatial heterogeneity, indicating early Mars' differentiated mantle. Volcanic outgassing plays avital role in the formation of the Martian climate, likely sustained water on the surface, influencing warm-wet or cold-dry conditions. Hesperian's favorable lithospheric heat flow (45 mW/m2) supports extended water existence, resembling Earth's conditions. Whereas, Amazonian's diminished heat flux (25 mW/m2) corresponds to water loss and arid climate. Hesperian's similar lithospheric thickness to mid-Noachian implies prolonged water retention, influencing climate and potential for astrobiological research, expanding perspectives for future Martian missions. Future work: As volcanism was active throughout its history. The emergence of Mars' extensive volcanic regions, known as large igneous provinces, which are linked to intermittent volcanic activity driven by mantle plumes, poses challenges to understanding the scale and persistence of these phenomena in Martian convection models. Therefore, understanding the regional-scale changes in eruptive processes within Martian volcanic provinces over time remains unclear and crucial for deciphering the evolution of the Martian interior without Earth-like plate tectonics. We will continue this work with petrological and thermoelastic analyses to study the compositional and spatiotemporal evolution of the Elysium Volcanic Province.

A Rani↗

Platinum group elements in a 3.5 Ga nickel-iron occurrence - Possible evidence of a deep mantle origin

This paper reports the results of new field observations and the geochemical analyses for the area of the Bon Accord (BA) (the Kaapvaal craton, South Africa) Ni-Fe deposit, with particular consideration given to the trace element, platinum-group element, and isotopic (Pb, Nd, and Os) compositions. On the basis of these data, an interpretation of BA is suggested, according to which the BA deposit is a siderophile-rich heterogeneity remaining in the deep mantle after a process of incomplete core formation. The implications of such a model for the study of core-mantle segregation and the geochemistry of the lowermost mantle are discussed.

Tredoux, Marian↗

Phase Equilibria of a S- and C-Poor Lunar Core

The composition of the lunar core can have a large impact on its thermal evolution, possible early dynamo creation, and physical state. Geochemical measurements have placed better constraints on the S and C content of the lunar mantle. In this study we have carried out phase equilibrium studies of geochemically plausible S- and C-poor lunar core compositions in the Fe-Ni-S-C system, and apply them to the early history of the Moon. We chose two bulk core compositions, with differing S and C content based on geochemical analyses of S and C trapped melts in Apollo samples, and on the partitioning of S and C between metal and silicate. This approach allowed calculation of core S and C contents - 90% Fe, 9% Ni, 0.5% C, and 0.375% S by weight; a second composition contained 1% each of S and C. Experiments were carried out from 1473K to 1973K and 1 GPa to 5 GPa, in piston cylinder and multi- anvil apparatuses. Combination of the thermal model of with our results, shows that a solid inner core (and therefore initiation of a dynamo) may have been possible in the earliest history of the Moon (approximately 4.2 Ga ago), in agreement with. Thus a volatile poor lunar core may explain the thermal and magnetic history of the Moon.

Righter, K.↗

Influence of Heat Flow from the Planetary Interior on Surface Habitability

an primordial and/or radiogenic heat flow from a rocky planet’s interior help maintain a surface environment amenable to life?On rocky Earth-like planets with shallow oceans (≤5 km depth) that are on the outer edge of the habitable zone, the additional energy provided might make the difference between a world supporting regional habitat space and a world uninhabitable by any known life-form. To test this hypothesis, we introduce heat flux from the planetary interior as a forcing to the NASA/GISSROCKE-3D exoplanet GCM, and explore whether it can enhance the habitability of marginal terrestrial rocky planets (e.g.,paleo Earth in a “snowball” climate state).GCM simulations of modern Earth have not included geothermal heat flux as a climate forcing, as it is more than an order of magnitude less than the 2.9 W/m heating caused by anthropogenic greenhouse gases [Flanner, GRL 2009]. Modern Earth measurements in the oceans [Downes et al., GRL 2019] and results from ocean GCMs [Barnes et al., Ocean Model. 2017]suggest that localized higher heat flux can have measurable thermodynamic and dynamic impacts, such as weakening deep ocean stratification and increased poleward ocean heat transports. A similar result with ROCKE-3D would be important, since our snowball Earth simulations without heat flux produce features like ocean stratification that should have hampered the survival of life. We have created a set of spatially variable geothermal heat fluxes at varying horizontal resolutions based on modern Earth heat flow patterns [Davies, Geochem. Geophys. Geosys. 2013] to test the sensitivity of the ROCKE-3D GCM initially in a modern Earth context. Preliminary results show that even modest heat fluxes have a measurable impact on deep ocean temperatures (upto +0.9°C locally) and that this heat can be transported at depth along ocean circulation paths. Estimates of heat flux impacts on vertical ocean mixing and surface ocean conditions require long simulations at the higher spatial resolutions needed to express heat flow at the scale of most ocean ridges. Ongoing simulations are focused on testing the impacts of horizontal resolution and flux scaling on surface environments, especially for “snowball” climate scenarios.

Heat flow↗

Lunar and Planetary Science XXXV: Mars Volcanology and Tectonics

Reports from the session, "Mars Volcanology and Tectonics" include:Martian Shield Volcanoes; Estimating the Rheology of Basaltic Lava Flows; A Model for Variable Levee Formation Rates in an Active Lava Flow; Deflections in Lava Flow Directions Relative to Topography in the Tharsis Region: Indicators of Post-Flow Tectonic Motion; Fractal Variation with Changing Line Length: A Potential Problem for Planetary Lava Flow Identification; Burfellshraun:A Terrestrial Analogue to Recent Volcanism on Mars; Lava Domes of the Arcadia Region of Mars; Comparison of Plains Volcanism in the Tempe Terra Region of Mars to the Eastern Snake River Plains, Idaho with Implications for Geochemical Constraints; Vent Geology of Low-Shield Volcanoes from the Central Snake River Plain, Idaho: Lessons for Mars and the Moon; Field and Geochemical Study of Table Legs Butte and Quaking Aspen Butte, Eastern Snake River Plain, Idaho: An Analog to the Morphology of Small Shield Volcanoes on Mars; Variability in Morphology and Thermophysical Properties of Pitted Cones in Acidalia Planitia and Cydonia Mensae; A Volcano Composed of Light-colored Layered Deposits on the Floor of Valles Marineris; Analysis of Alba Patera Flows: A Comparison of Similarities and Differences Geomorphologic Studies of a Very Long Lava Flow in Tharsis, Mars; Radar Backscatter Characteristics of Basaltic Flow Fields: Results for Mauna Ulu, Kilauea Volcano, Hawaii;and Preliminary Lava Tube-fed Flow Abundance Mapping on Olympus Mons.

Source record↗

Germanium Enrichments in Sedimentary Rocks in Gale Crater, Mars: Constraining the Timing of Alteration and Character of the Protolith

Rocks enriched in Ge have been discovered in Gale Crater, Mars, by the Alpha-particle X-ray spectrometer (APXS) on the Mars Science Lab (MSL) rover, Curiosity. The Ge concentrations in Gale Crater (commonly >50 ppm) are remarkably high in comparison to Earth, where Ge ranges from 0.5-4.0 ppm in igneous rocks and 0.2-3.3 ppm in siliciclastic sediment. Primary meteoritic input is not likely the source of high Ge because Ge/Ni in chondrites (approx.0.003) and irons (<0.04) is lower than in Gale rocks (0.08-0.2). Earth studies show Ge is a useful geochemical tracer because it is coherent with Si during magmatic processes and Ge/Si varies less than 20% in basalts. Ge and Si fractionate during soil/regolith weathering, with Ge preferentially sequestered in clays. Ge is also concentrated in Cu- and Zn-rich hydrothermal sulfide deposits and Fe- and Mnrich oxide deposits. Other fluid-mobile elements (K, Zn, Cl, Br, S) are also enriched at Gale and further constrain aqueous alteration processes. Here, we interpret the sediment alteration history and present a possible model for Ge enrichments at Gale involving fluid alteration of the protolith.

Berger, J. A.↗

The contribution of Alaskan, Siberian, and Canadian coastal polynas to the cold halocline layer of the Arctic Ocean

Numerous Arctic Ocean circulation and geochemical studies suggest that ice growth in polynyas over the Alaskan, Siberian, and Canadian continental shelves is a source of cold, saline water which contributes to the maintenance of the Arctic Ocean halocline. The purpose of this study is to estimate for the 1978-1987 winters the contributions of Arctic coastal polynyas to the cold halocline layer of the Arctic Ocean. The study uses a combination of satellite, oceanographic, and weather data to calculate the brine fluxes from the polynyas; then an oceanic box model is used to calculate their contributions to the cold halocline layer of the Arctic Ocean. This study complements and corrects a previous study of dense water production by coastal polynyas in the Barents, Kara, and Laptev Seas.

Cavalieri, Donald J.↗

Abundances and Distributions of Volatile Elements (Na, S, Cl, K) Within Lunar Volcanic Glass Spheres

This research developed and applied high-precision analytical methods (electron microprobe) to determine the major- and minor-element abundances (Si, Ti, A], Cr, Fe, Mn, Mg, Ca, Na, K) in three suites of Apollo 14 volcanic green glasses. Since the precision of these data was a factor of 5-10 better than previously published results, the data provided the strongest constraints yet achieved on the geochemical processes that operated at depths less than 400 kilometers inside the Moon. The results of this work were submitted to the 29th Lunar and Planetary Science Conference, formed the basis for a Master's Thesis, and were published in the top-tier geochemical journal. Additional high-precision data on the trace abundances of sodium (Na), sulfur (S), and potassium (K) in the Apollo 17 volcanic orange glasses (74220) were also acquired during this grant-period. These data show diffusion profiles within individual 200-micron diameter, glass spherules that were apparently generated during the fire-fountain eruption of this magma in the presence of a transient vapor phase. Although these results have not yet been published, publication is planned in 2001 after additional numerical modeling has been completed. This work has also catalyzed on-going collaborative work with Professor Timothy Grove (MIT) to analyze and understand the origin of the Apollo 15 volcanic green glasses. That work will be completed for publication in 2001.

Delano, John W.↗

Collapse of the Late Proterozoic ecosystem

Evidence accumulated over the past two decades is now sufficient to permit an initial quantitative assessment of the patterns of biotic diversity and extinction that occurred during Proterozoic time. Because of limitations in both the quality and quantity of data currently available, however, generalizations thus derived must be regarded as tentative. Nevertheless, read literally, available palaeontological data appear to indicate that the global ecosystem experienced a gradual but massive collapse between 1 000 Ma and the beginning of the Phanerozoic, a supposition consistent with other lines of geological and geochemical evidence. A possible forcing agent for such a collapse appears to have been a decrease in ambient levels of carbon dioxide and a resultant decrease in average global temperature, photosynthetic efficiency, and primary productivity.

NASA Discipline Exobiology↗

Os-186 and Os-187 Enrichments and High-He-3/He-4 sources in the Earth's Mantle: Evidence from Icelandic Picrites

Picrites from the neovolcanic zones in Iceland display a range in Os-187/Os-188O from 0.1297 to 0.1381 ((gamma)Os = 0.0 to 6.5) and uniform Os-186/Os-188 of 0.1198375+/-32 (2 (sigma)). The value for Os-186/Os-188 is within uncertainty of the present-day value for the primitive upper mantle of 0.1198398+/-16. These Os isotope systematics are best explained by ancient recycled crust or melt enrichment in the mantle source region. If so, then the coupled enrichments displayed in Os-186/Os-188 and Os-187/Os-188 from lavas of other plume systems must result from an independent process, the most viable candidate at present remains core-mantle interaction. While some plumes with high He-3/He-4, such as Hawaii, appear to have been subjected to detectable addition of Os (and possibly He) from the outer core, others such as Iceland do not. A positive correlation between Os-187/Os-188 and He-3/He-4 from 9.6 to 19 RA in Iceland picrites is best modeled as mixtures of 500 Ma or older ancient recycled crust mixed with primitive mantle, creating a hybrid source region that subsequently mixes with the convecting MORB mantle during ascent and melting. This multistage mechanism to explain these isotope systematics is consistent with ancient recycled crust juxtaposed with more primitive, relatively He-rich mantle, in convective isolation from the upper mantle, most likely in the lowermost mantle. This is inconsistent with models that propose random mixing between heterogeneities in the convecting upper mantle as a mechanism to explain the observed isotopic variation in oceanic lavas or models that produce a high He-3/He-4 signature in melt depleted and strongly outgassed, He-poor mantle. Instead these systematics require a deep mantle source to explain the 3He/4He signature in Iceland lavas. The He-3/He-4 of lavas derived from the Iceland plume changed over time, from a maximum of 50 RA at 60 Ma, to approximately 25-27 RA at present. The changes are coupled with distinct compositional gaps between the different aged lavas when H-3/He-4 is plotted versus various geochemical parameters such as Nd-143/Nd-144 and La/Sm. These relationships can be interpreted as an increase in the proportion of ancient recycled crust in the upwelling plume over this time period.

Brandon, Alan D.↗

Constraints on hydrothermal heat flux through the oceanic lithosphere from global heat flow

A significant discrepancy exists between the heat flow measured at the seafloor and the higher values predicted by thermal models of the cooling lithosphere. This discrepancy is generally interpreted as indicating that the upper oceanic crust is cooled significantly by hydrothermal circulation. The magnitude of this heat flow discrepancy is the primary datum used to estimate the volume of hydrothermal flow, and the variation in the discrepancy with lithospheric age is the primary constraint on how the hydrothermal flux is divided between near-ridge and off-ridge environments. The resulting estimates are important for investigation of both the thermal structure of the lithosphere and the chemistry of the oceans. We reevaluate the magnitude and age variation of the discrepancy using a global heat flow data set substantially larger than in earlier studies, and the GDHI (Global Depth and Heat Flow) model that better predicts the heat flow. We estimate that of the predicted global oceanic heat flux of 32 x 10(exp 12) W, 34% (11 x 10(exp 12) W) occurs by hydrothermal flow. Approximately 30% of the hydrothermal heat flux occurs in crust younger than 1 Ma, so the majority of this flux is off-ridge. These hydrothermal heat flux estimates are upper bounds, because heat flow measurements require sediment at the site and so are made preferentially at topographic lows, where heat flow may be depressed. Because the water temperature for the near-ridge flow exceeds that for the off-ridge flow, the near-ridge water flow will be even a smaller fraction of the total water flow. As a result, in estimating fluxes from geochemical data, use of the high water temperatures appropriate for the ridge axis may significantly overestimate the heat flux for an assumed water flux or underestimate the water flux for an assumed heat flux. Our data also permit improved estimates of the 'sealing' age, defined as the age where the observed heat flow approximately equals that predicted, suggesting that hydrothermal heat transfer has largely ceased. Although earlier studies suggested major differences in sealing ages for different ocean basins, we find that the sealing ages for the Atlantic, Pacific, and Indian oceans are similar and consistent with the sealing age for the entire data set, 65 +/- 10 Ma. The previous inference of a young (approximately 20 Ma) sealing age for the Pacific appears to have biased downward several previous estimates of the global hydrothermal flux. The heat flow data also provide indirect evidence for the mechanism by which the hydrothermal heat flux becomes small, which has often been ascribed to isolation of the igneous crust from seawater due to the hydraulic conductivity of the intervening sediment. We find, however, that even the least sedimented sites show the systematic increase of the ratio of observed to predicted heat flow with age, although the more sedimented sites have a younger sealing age. Moreover, the heat flow discrepancy persists at heavily sedimented sites until approximately 50 Ma. It thus appears that approximately 100-200 m of sediment is neither necessary nor sufficient to stop hydrothermal heat transfer. We therefore conclude that the age of the crust is the primary control on the fraction of heat transported by hydrothermal flow and that sediment thickness has a lesser effect. This inference is consistent with models in which hydrothermal flow decreases with age due to reduced crustal porosity and hence permeability.

Stein, Carol A.↗

Geochemical evidence bearing on the origin of aerobiosis, a speculative hypothesis

It is pointed out that the atmosphere and hydrosphere of the early Archean earth were essentially anoxic. The paleontological record shows that life existed in spite of the absence of oxygen. The present investigation is concerned with the presentation of a plausible sequence of events, linking features in the carbon isotopic record to the origin of oxygenic photosynthesis. The investigation takes into account that the record of carbon isotopic abundances in sedimentary organic matter displays marked variations about 2.8 Ga before the present. At least by 2.8 Ga before the present, if not before, something in the carbon cycle began to allow the incorporation in sediments of organic material extraordinarily depleted in C-13. Attention is given to a model for the development of C-13 depleted kerogens, conclusions regarding the late Archean carbon cycle, and the transition in the global ecosystem.

Hayes, J. M.↗

Chromium on Mercury: New Results From the MESSENGER X-Ray Spectrometer and Implications for the Innermost Planet’s Geochemical Evolution

Mercury, the innermost planet, formed under highly reduced conditions, based mainly on surface Fe, S, and Si abundances determined from MESSENGER mission data. The minor element Cr may serve as an independent oxybarometer but only very limited Cr data have been previously reported for Mercury. We report Cr/Si abundances across Mercury's surface based on MESSENGER X-Ray Spectrometer data throughout the spacecraft's orbital mission. The heterogeneous Cr/Si ratio ranges from 3.6 × 10 -5 in the Caloris Basin to 0.0012 within the high-magnesium region, with an average southern hemisphere value of 0.0008 (corresponding to about 200 ppm Cr). Absolute Cr/Si values have systematic uncertainty of at least 30%, but relative variations are more robust. By combining experimental Cr partitioning data along with planetary differentiation modeling, we find that if Mercury formed with bulk chondritic Cr/Al, Cr must be present in the planet's core and differentiation must have occurred at log ƒO 2 in the range of IW-6.5 to IW-2.5 in the absence of sulfides in its interior and a range of IW-5.5 to IW-2 with an FeS layer at the core-mantle boundary. Models with large fractions of Mg-Ca-rich sulfides in Mercury's interior are more compatible with moderately reducing conditions (IW-5.5 to IW-4) owing to the instability of Mg-Ca-rich sulfides at elevated ƒO 2 . These results indicate that if Mercury differentiated at a log ƒO 2 lower than IW-5.5, the presence of sulfides whether in the form of a FeS layer at the top of the core or Mg-Ca-rich sulfides within the mantle would be unlikely.

Larry R. Nittler↗

Discovery Venera surface: Atmosphere geochemistry experiments mission concept

The phenomenal increase in our understanding of Venus provided by the Magellan Mission has raised a series of focused, fundamental scientific questions about the geochemistry of the surface of Venus, the nature of the lower atmosphere, and the relationship of the lower atmosphere and surface. First, surface geochemical measurements from the Venera/Vega spacecraft showed that widely spaced regions of the venusian plains are made of basalts; thus basalts are significant and may be the only component of the venusian crust. But we lack information on the composition of several key elements of Venus geology: (1) Tessera terrain (which may be outcrops of continental-like non-basaltic crustal material) and steep-sided domes/festoons are promising candidates for non-basaltic geochemically evolved material. The composition of the lower part of the Venusian crust is unknown: however, ejecta from large venusian craters provides us with the possibility of sampling this material on the surface; (2) bulk chemistry (structure and dynamics) of the venusian atmosphere are known. The altitude profiles of water vapor content and minor admixtures relevant to redox conditions in the lower atmosphere (less than 20 km altitude) remain uncertain. Lack of that knowledge means that we do not understand the fine chemical structure of the main mass of the Venusian atmosphere; and (3) thermodynamic models predict that igneous materials on the surface of Venus should react with gases of the venusian atmosphere. But because the water vapor content and redox conditions in the lower atmosphere are not well known, we do not understand the nature of venusian weathering: oxidation, sulfatization, carbonatization, and hydration. The answers to these questions are critical to the understanding of Venus, the most Earth-like of the terrestrial planets.

Surkov, Yuri A.↗

Potassium-bearing Iron-Nickel Sulfides in Nature and High-Pressure Experiments: Geochemical Consequences of Potassium in the Earth's Core

Introduction: Potassium (K) as a large ion lithophile element has dominantly been concentrated in the Earth s crust and the mantle through differentiation, and in the form of K-40 contributes to the planet s heat budget. However, whether or not K also enters core-forming phases, has been debated for over three decades. Arguments favoring entry of K in the core are based on: (1) K-sulfide (with Fe, Ni, Cu, Na, and Cl; djerfisherite) found in highly reduced enstatite chondrites (or aubrites, enstatite achondrites); (2) demonstration that K, owing to an s-d electronic switch at high-pressure, exhibits transition- element like character, (3) solubility of measurable K in Fe-Ni-S liquids at high pressure, temperature conditions, and (4) models of cooling of the core that seem to require, besides convection, some form of radioactivity, and thus lending support to the experimental work. In this contribution, we assess the effect of sequestering K in the core, as it is perhaps an element that is a key to reconciling geochemistry, paleomagnetism, accretion, and thermal evolution models for the planet.

Keshav, S.↗

A Simulated Geochemical Rover Mission to the Taurus-Littrow Valley of the Moon

We test the effectiveness of using an alpha backscatter, alpha-proton, X ray spectrometer on a remotely operated rover to analyze soils and provide geologically useful information about the Moon during a simulated mission to a hypothetical site resembling the Apollo 17 landing site. On the mission, 100 soil samples are "analyzed" for major elements at moderate analytical precision (e.g., typical relative sample standard deviation from counting statistics: Si[11%], Al[18%], Fe[6%], Mg[20%], Ca[5%]). Simulated compositions of soils are generated by combining compositions of components representing the major lithologies occurring at the site in known proportions. Simulated analyses are generated by degrading the simulated compositions according to the expected analytical precision of the analyzer. Compositions obtained from the simulated analyses are modeled by least squares mass balance as mixtures of the components, and the relative proportions of those components as predicted by the model are compared with the actual proportions used to generate the simulated composition. Boundary conditions of the modeling exercise are that all important lithologic components of the regolith are known and are represented by model components, and that the compositions of these components are well known. The effect of having the capability of determining one incompatible element at moderate precision (25%) is compared with the effect of the lack of this capability. We discuss likely limitations and ambiguities that would be encountered, but conclude that much of our knowledge about the Apollo 17 site (based on the return samples) regarding the distribution and relative abundances of lithologies in the regolith could be obtained. This success requires, however, that at least one incompatible element be determined.

Korotev, Randy L.↗

A Transmission Electron Microscopy Study of a Refractory Metal Grain from a Calcium-Aluminum-Rich Inclusion in the Leoville CV3 Chondrite

Introduction: Calcium-aluminum-rich inclusions (CAIs) are an important component of chondritic meteorites. They can contain materials that are thermodynamically predicted and isotopically age dated to be among the first-formed solids in our solar system [1-5]. Observed in some CAIs are micron to sub-micron sized inclusions rich in Fe, Ni, and high-Z elements such as Pt, Os, Ir and W, in the form of refractory metal nuggets (RMNs), fremdlinges, and ‘nugget like objects’ (NLOs) [1,6]. Refractory siderophile elements such as Os, Ir and Ru are thermodynamically predicted to condense at temperatures well in excess of the major CAI phases such as melilite, perovskite, spinel and hibonite [2,7-9]. These refractory metal inclusions in CAIs can therefore serve as probes into the thermodynamic landscape of the early solar protoplanetary disk. Here we report on a refractory grain identified in a CAI of the Leoville CV3 chondrite. This work is part of an ongoing effort to gain insight into the thermochemistry of the early solar system through systematic analyses of the structure and chemistry of various components in CAIs [10-13]. Sample and Analytical Techniques: A fluffy type A CAI (Fig. 1A) was identified in a section of the Leoville, CV3 chondrite (Center for Meteorite Studies, Arizona State University collection, #821_C_3) using a JOEL-JXA 8530F electron microprobe at Arizona State University. Backscattered electron (BSE) imaging and energy-dispersive X-ray spectroscopy (EDS) were used to identify refractory metal grains in the CAI using a Thermo Fisher (formerly FEI) Helios NanoLab 660 G3 focused-ion-beam scanning-electron microscope (FIBSEM) located at the Kuiper Materials Imaging and Characterization Facility (KMICF) at the Lunar and Planetary Laboratory, University of Arizona. The FIB is equipped with an EDAX EDS system. We selected one of the larger (micron-sized) refractory metal grains, designated as ‘Spud’ (Fig. 1B) for further analysis. ‘Spud’ was extracted and thinned to electron transparency (<100 nm) using the FIB-SEM located in KMICF, following methods described by [14- 15]. The FIB section was analyzed using a 200 keV Hitachi HF5000 scanning transmission electron microscope (S/TEM) located at KMICF. The HF5000 is equipped with cold-field emission gun, 3rd-order spherical aberration corrector for STEM imaging, and an Oxford Instruments X-Max N 100 TLE energydispersive spectroscopy (EDS) system with dual 100 mm2 windowless silicon-drift detectors (Ω = 2.0 sr). Selected-area electron-diffraction (SAED) patterns were acquired to aid in determination of crystallinity and phase. Results: The mineralogy, texture, and morphology of the CAI are consistent with that of a fluffy type A (FTA) CAI [16]. BSE imaging at high magnifications revealed grains with high contrast, indicative of compositions rich in elements of higher atomic number relative to surrounding material. These high-Z grains have sizes that range from ∼250 nm to 4 µm. EDS analyses confirm that the bright grains are metal-rich inclusions. A minor fraction of the grains are composed of only Fe and Ni, but the majority (∼60%) of the identified inclusions also contained various refractory siderophiles including Os, Ru, Zr, Ir and Mo. EDS analysis on the FIB-SEM of Spud shows that it contains Fe, Ni, Mo and Ru. High-angle annular dark-field (HAAFD) imaging and EDS mapping in the TEM (Fig. 2) show that Spud occurs in melilite (Ca1.9Al1.99Si1.06O7). Spud contains a subhedral to anhedral morphology and is compositionally heterogenous (polyphasic, Fig. 2). Local spatial correlation occurs among Fe, Ni, and Pt, and also among Os, Ru, and Mo. SAED patterns show that the Fe-Ni-Pt, Fe-Os-Mo-Ru and Fe-Pt regions are crystalline. Discussion: CAIs can contain various types of inclusions rich in Fe, Ni and refractory siderophiles such as Os, Ru, W and Pt [1]. RMNs are micron-sized, single phase alloy grains and can contain Os, Ir, Ru and Rh [1,7,17]. NLOs are also micron-sized inclusions, but contain two phases, a refractory metal, and an oxide [6]. Fremdlinge are the largest of such inclusions (tens of microns in size) and are complex aggregates of Fe-Ni alloy, silicates, oxides, and sulfides [1,17]. While the size of Spud matches previous descriptions of RMNs and NLOs, Spud is neither a single-phase alloy like RMNs, nor does it contain one metal phase and one oxide like NLOs. Spud does not match the above described categories of refractory metal inclusions. The presence of refractory siderophiles such as Mo, Os, Ru, and Pt suggests a high-temperature origin. Thermodynamic modelling by [7] indicates condensation temperatures of 1917 K, 1693 K, 1613 K and 1415 K for Os, Mo, Ru and Pt respectively. These models also show that following the initial condensation of a refractory metal, alloying of solutes such as Fe, Ni and W, occurs in levels proportional to their partial pressures in the surrounding gas. Such alloying occurs at temperatures above the condensation temperatures of common CAI phases such as melilite (1529 K), perovskite (1441 K), spinel (197 K) and forsterite (1354 K) [2]. The polyphasic nature of Spud could be the result of such high-temperature alloying, possibly shortly after the condensation of Mo and Ru at 1693 K and 1613 K respectively. That Spud occurs as an inclusion is consistent with it having formed prior to and at temperature above that of its host melilite in this FTA CAI, which is qualitatively consistent with such prior thermodynamic modeling. Further, the polyphasic nature of Spud is similar to refractory grains from a FTA CAI in the Northwest Africa (NWA) 8323, CV3 chondrite [11-13]. These data suggest that such refractory metal grains could have been widespread in the inner and early solar protoplanetary disk and represent some of the earliest formed solids to have condensed. Acknowledgments: Research and instrumentation supported by NASA grants #NNX12AL47G, #NNX15AJ22G and #80NSSC19K0509, and NSF grants #1531243 and #0619599. Fig 2. STEM data on ‘Spud’. HAADF Image (Top) False-color EDS Maps (Bottom) References: [1] MacPherson G. J. (2014) T. of Geochem. Vol I: Met. And Cosmochem. Processes, 139-179. [2] Lodders K. (2003) ApJ, 591, 1220-1247. [3] Ebel D. S. (2006) Met. & the Early S. Sys. II., 253- 277. [4] Amelin Y. (2002) Science, 297, 1678-1683. [5] Connelly J.N. et.al. (2012) Science, 338, 651-655. [6] Schwander D. et al. (2015) GCA, 18, 70-87. [7] Palme H. and Wlotzka F. (1976) EPSL, 33, 45-60. [8] Berg T. et al. (2009) ApJ, 702, 172-176. [9] Liffman K. et al. (2021) Icarus, 221, 89-105. [10] Zega T.J. et al. (2021) PSJ, 2, 115. [11] Ramprasad T. et al. (2020) LPSC LI, Abstract #2472. [12] Ramprasad T. et al. (2021) Microscopy & Microanalysis, S1, 2792-2794. [13] Ramprasad T. et al. (2021) 84th MetSoc, Abstract #6123. [14] Zega T.J. et al. (2007) MAPS, 42, 1373-1386. [15] Ramprasad T. et al. (2022) MAPS, in revision. [16] Grossman L. (1975), GCA, 39, 433-454. [17] El Goresy A. et al. (1978) LPSC IX, Abstract#1100

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