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At least 613 records · Page 34

Characterization of Meteorites by Focused Ion Beam Sectioning: Recent Applications to CAIs and Primitive Meteorite Matrices

Focused ion beam (FIB) sectioning has revolutionized preparation of meteorite samples for characterization by analytical transmission electron microscopy (TEM) and other techniques. Although FIB is not "non-destructive" in the purest sense, each extracted section amounts to no more than nanograms (approximately 500 cubic microns) removed intact from locations precisely controlled by SEM imaging and analysis. Physical alteration of surrounding material by ion damage, fracture or sputter contamination effects is localized to within a few micrometers around the lift-out point. This leaves adjacent material intact for coordinate geochemical analysis by SIMS, microdrill extraction/TIMS and other techniques. After lift out, FIB sections can be quantitatively analyzed by electron microprobe prior to final thinning, synchrotron x-ray techniques, and by the full range of state-of-the-art analytical field-emission scanning transmission electron microscope (FE-STEM) techniques once thinning is complete. Multiple meteorite studies supported by FIB/FE-STEM are currently underway at NASA-JSC, including coordinated analysis of refractory phase assemblages in CAIs and fine-grained matrices in carbonaceous chondrites. FIB sectioning of CAIs has uncovered epitaxial and other overgrowth relations between corundum-hibonite-spinel consistent with hibonite preceding corundum and/or spinel in non-equilibrium condensation sequences at combinations of higher gas pressures, dust-gas enrichments or significant nebular transport. For all of these cases, the ability of FIB to allow for coordination with spatially-associated isotopic data by SIMS provides immense value for constraining the formation scenarios of the particular CAI assemblage. For carbonaceous chondrites matrix material, FIB has allowed us to obtain intact continuous sections of the immediate outer surface of Murchison (CM2) after it has been experimentally ion processed to simulate solar wind space weathering. The surface amorphization and loss of OH produced by the irradiation provides important clues regarding space weathering on primitive asteroids such as the OSIRIS-Rex target 101955 Bennu.

Christoffersen, Roy↗

Weathering in the Forelands of Two Rapidly Retreating Alpine Glaciers of Volcanic Bedrock in the Three Sisters, Oregon, USA

The glaciers of the Three Sisters volcanoes in Cascadia have retreated dramatically over the past century. In order to understand ongoing chemical weathering and solute transport in the proglacial valleys, waters were sampled from glacier outwash streams, local snowmelt, and proglacial springs and lakes at Collier and Diller Glaciers. To understand weathering and transport processes in the proglacial plains, infrared orbital remote sensing data was used to map compositional variability and highlight weathering products, which were then ground-truthed with laboratory mineralogical and chemical analyses of sediments. The hydrochemistry is significantly affected by a sub- and proglacial mafic weathering system lacking carbonate minerals. Here we report major ion concentrations in meltwaters for the summer 2016 and 2017 melt seasons. Total cation concentrations range from 3 to 250 μeq/l and dissolved bicarbonate concentrations range from 2 to 200 μeq/l. Other dissolved anions are negligible compared to bicarbonate. Dissolved silica concentrations range from 2 to 260 μmol/l, comparable to total dissolved cation concentrations. The highest cation and silica concentrations were measured in moraine-sourced springs. Compositional remote sensing analysis identified alteration zones in the proglacial plains at both Collier and Diller indicating potential hydrated silica. This analysis is consistent with laboratory analysis of sediment samples, which indicate the presence of poorly crystalline phases weathering products, including hydrated silica. Weathered materials are preferentially deposited on moraines due to aeolian and glacial transport, as well as intra-moraine alteration, and at abandoned stream terraces due to fluvial transport. Geochemical measurements indicate that the predominant form of chemical weathering in these periglacial mafic systems is the carbonation of feldspar as well as reactive volcanic glass. The presence of poorly crystalline silicates, as indicated by remote sensing datasets and laboratory analysis, is consistent with rapid weathering of feldspars and glass and formation of Fe-Al-Si-bearing mineraloids in these proglacial valleys. This weathering regime has wide-ranging implications for atmospheric CO2 drawdown due to cold-climate volcanic rock weathering.

Rutledge, Alicia M.↗

Temperature effects on cobalt hydroxide–cobalt carbonate competitive growth on carbonate surfaces

Cobalt (Co), a critical metal essential for various environmental and industrial processes, undergoes speciation and immobilization in natural systems, primarily interacting with existing mineral surfaces. Understanding the underlying mechanisms of Co immobilization on abundant carbonate surfaces under different environmental conditions is critical for predicting Co mobility, availability, and recovery. In this study, we investigated the temperature-dependent competition between CoCO 3 and Co(OH) 2 formation on calcite (CaCO 3 ) and magnesite (MgCO 3 ) surfaces. Using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS), we analyzed carbonate substrates exposed to CoCl 2 solutions at varying concentrations (0–500 μM) and temperatures (22, 50, and 80 °C). Magnesite surfaces promoted CoCO 3 formation due to its low lattice mismatch with sphaerocobaltite (CoCO 3 ). However, this slow-growing CoCO 3 component was progressively outcompeted by Co(OH) 2 formation as the temperature and/or initial Co concentration increased. On calcite surfaces, the poor lattice mismatch between calcite and sphaerocobaltite led to Co(OH) 2 outcompeting CoCO 3 formation at all three temperatures. These findings provide critical insights into the roles of substrate composition, solution chemistry, and temperature in controlling Co speciation and mobility. They carry important implications for environmental transport, geochemical cycling, and industrial recovery of cobalt in carbonate-rich systems.

Calcite↗

Raw Data published in PeerJ, 2021 for Crested Butte decomposition field study 2017-2019.

This data package contains text files that describe geochemical measurements collected from 2017-2019 during isolated conifer needle decomposition field studies in Crested Butte, Colorado. The geochemical measurements were collected across three elevations (2,800–3,500 m) ranging from montane to subalpine ecoregions. The data sets within include total carbon and nitrogen content and fourier-transform infrared spectroscopy (FTIR) results for the initial needles collected in 2016 and after decomposition in 2019. Data collection results from August 2020 are also included from when the experimental plots were removed to understand final concentrations of soil extractable carbon and nitrogen content as well as mass balances from litter bag deployments. Soil porewater results are also provided from 2017-2019 for DOC, TN, UV254, and specific UV absorbance (SUVA) analyses at 15 cm soil depth. Gas flux raw data provides CO2, CH4, N2O, and NH3 measurements above needle decomposition over the three study years. Finally, soil samples for microbial DNA extractions were collected from the upper soil depth. This raw data is available in the NCBI SRA database under SRA accession numbers PRJNA605259 and PRJNA715914. These data sets were generated to investigate the isolated decomposition of spruce and lodgepole conifer needles. The goal of this work was to determine the roles of elevation, soil type, seasonal changes in soil moisture, and snowmelt timing on litter decomposition processes. Results from this work are detailed in the reference paper "Effect of elevation, season and accelerated snowmelt on biogeochemical processes during isolated conifer needle litter decomposition. DOI: 10.7717/peerj.11926."

54 ENVIRONMENTAL SCIENCES↗

Microtopographic and Depth Controls on Active Layer Chemistry in Arctic Polygonal Ground: Supporting Data

Polygonal ground is a signature characteristic of the Arctic, and permafrost thaw can potentially generate substantial feedbacks to Arctic ecosystems and climate. This study describes the first comprehensive spatial examination of active layer biogeochemistry that extends across high- and low-centered polygons and their features, including depth. Water chemistry measurements were made on active layer water samples collected near Barrow, Alaska during summer, 2012. Several significant differences in chemistry were observed between high- and low-centered polygons suggesting polygon types may be useful for landscape-scale geochemical classification. However, differences were found for polygon features (centers and troughs) for analytes that were not significant for type, suggesting that finer scale features control biogeochemistry in a different way than polygon type. Depth variations were also significant, demonstrating important multi-dimensional aspects of polygonal ground biogeochemistry. These results have major implications for understanding how polygonal ground ecosystems function, and how they may respond to future change. This data package includes one *.csv data file and one *.pdf user guide. The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

Analyzers Measure Greenhouse Gases, Airborne Pollutants

In complete darkness, a NASA observatory waits. When an eruption of boiling water billows from a nearby crack in the ground, the observatory s sensors seek particles in the fluid, measure shifts in carbon isotopes, and analyze samples for biological signatures. NASA has landed the observatory in this remote location, far removed from air and sunlight, to find life unlike any that scientists have ever seen. It might sound like a scene from a distant planet, but this NASA mission is actually exploring an ocean floor right here on Earth. NASA established a formal exobiology program in 1960, which expanded into the present-day Astrobiology Program. The program, which celebrated its 50th anniversary in 2010, not only explores the possibility of life elsewhere in the universe, but also examines how life begins and evolves, and what the future may hold for life on Earth and other planets. Answers to these questions may be found not only by launching rockets skyward, but by sending probes in the opposite direction. Research here on Earth can revise prevailing concepts of life and biochemistry and point to the possibilities for life on other planets, as was demonstrated in December 2010, when NASA researchers discovered microbes in Mono Lake in California that subsist and reproduce using arsenic, a toxic chemical. The Mono Lake discovery may be the first of many that could reveal possible models for extraterrestrial life. One primary area of interest for NASA astrobiologists lies with the hydrothermal vents on the ocean floor. These vents expel jets of water heated and enriched with chemicals from off-gassing magma below the Earth s crust. Also potentially within the vents: microbes that, like the Mono Lake microorganisms, defy the common characteristics of life on Earth. Basically all organisms on our planet generate energy through the Krebs Cycle, explains Mike Flynn, research scientist at NASA s Ames Research Center. This metabolic process breaks down sugars for energy to fuel cellular functions. "We think this chemical process did not exist when life first formed on Earth," he says, "because it is based on oxygen being available, and there was little oxygen available on the early Earth." It is possible that there are anaerobic regions beneath the sea floor in which life forms like those early non-Krebs Cycle microbes may yet exist. To detect and potentially collect samples of life emerging from hydrothermal vents, Flynn and his colleagues created Medusa, a multi-sensor instrument designed for long-term observation of diked vents on the ocean floor. When the vents erupt, Medusa assesses indicators of life within the expelled water. If the results are positive, the observatory collects samples and detaches from the ocean floor, making the long journey to the surface for retrieval by scientists. One of the indicators Medusa measures is the ratio of carbon isotopes in the water, namely carbon-12 and carbon-13. Living organisms preferentially take up carbon-12, Flynn says, so examining the ratio of these isotopes can help to determine the source of carbon in an environment as either biological or non-biological. "On Mars, there is evidence of localized methane in the atmosphere, and that methane could come from biological sources or from geochemical ones," Flynn says. "Determining the background planetary carbon isotope ratios and then evaluating the specific carbon ratios in this methane would help to determine how it was formed." A long-duration observatory similar to Medusa could one day provide essential evidence for or against the presence of life on the Red Planet or beneath the ice-crusted oceans of Europa.

Source record↗

Evidence of cryptic methane cycling and non-methanogenic methylamine consumption in the sulfate-reducing zone of sediment in the Santa Barbara Basin, California

The recently discovered cryptic methane cycle in the sulfate-reducing zone of marine and wetland sediment couples methylotrophic methanogenesis to anaerobic oxidation of methane (AOM). Here we present evidence of cryptic methane cycling activity within the upper regions of the sulfate-reducing zone, along a depth transect within the Santa Barbara Basin, off the coast of California, USA. The top 0–20 cm of sediment from each station was subjected to geochemical analyses and radiotracer incubations using 35 S–SO$^{2-}_{4}$, 14 C–mono-methylamine, and 14 C–CH 4 to find evidence of cryptic methane cycling. Methane concentrations were consistently low (3 to 16 µM) across the depth transect, despite AOM rates increasing with decreasing water depth (from max 0.05 nmol cm -3 d -1 at the deepest station to max 1.8 nmol cm -3 d -1 at the shallowest station). Porewater sulfate concentrations remained high (23 to 29 mM), despite the detection of sulfate reduction activity from 35 S–SO$^{2-}_{4}$ incubations with rates up to 134 nmol cm -3 d -1 . Metabolomic analysis showed that substrates for methanogenesis (i.e., acetate, methanol and methylamines) were mostly below the detection limit in the porewater, but some samples from the 1–2 cm depth section showed non-quantifiable evidence of these substrates, indicating their rapid turnover. Estimated methanogenesis from mono-methylamine ranged from 0.2 to 0.5 nmol cm -3 d -1 . Discrepancies between the rate constants (k) of methanogenesis (from 14 C–mono-methylamine) and AOM (from either 14 C–mono-methylamine-derived 14 C–CH 4 or from directly injected 14 C–CH 4 ) suggest the activity of a separate, concurrent metabolic process directly metabolizing mono-methylamine to inorganic carbon. We conclude that the results presented in this work show strong evidence of cryptic methane cycling occurring within the top 20 cm of sediment in the Santa Barbara Basin. The rapid cycling of carbon between methanogenesis and methanotropy likely prevents major build-up of methane in the sulfate-reducing zone. Furthermore, our data suggest that methylamine is utilized by both methanogenic archaea capable of methylotrophic methanogenesis and non-methanogenic microbial groups. We hypothesize that sulfate reduction is responsible for the additional methylamine turnover, but further investigation is needed to elucidate this metabolic activity.

54 ENVIRONMENTAL SCIENCES↗

Distribution of nickel(II) ions adsorbed at the muscovite mica (001)-water interface determined by in-situ resonant anomalous X-ray reflectivity

Mineral-water interfaces mediate adsorption, ion exchange, and secondary mineral formation that control element mobility in natural and engineered systems. Reliable prediction and control of these processes require a fundamental understanding of the interfacial structure that links adsorbed ion speciation to macroscopic sorption capacity and strength. Here, we determine atomic-scale changes in hydration and distribution of Ni(II) at the muscovite mica (001)-water interface using in situ high-resolution X-ray reflectivity (XR) and resonant anomalous X-ray reflectivity (RAXR) at 1 mM NiCl2 and pH 5.7. XR reveals reorganization of the primary hydration structure relative to that in deionized water: the water layer adsorbed in the cavity sites at a height of ~1.3 Å disappears, while distinct solution layers emerge at ~2.3, ~4.1, and ~5.6 Å above the basal oxygen plane. RAXR resolves three interfacial Ni(II) species: a dominant outer-sphere complex at 3.65 Å (~80% of the total coverage), a minor inner-sphere complex at 0.75 Å, and a low-coverage, more distant outer-sphere species at 5.63 Å. These three adsorbed Ni(II) species account for a total Ni(II) coverage of 0.54 ± 0.02 ion per unit cell area that compensates for the surface charge. These results highlight the role of interfacial hydration in controlling the speciation and stability of adsorbate cations on the negatively charged mica surface, providing quantitative insight into predicting the geochemical behavior of divalent metal cations in the aqueous environments.

Lee, Sang Soo↗

Melting of the Primitive Mercurian Mantle, Insights into the Origin of Its Surface Composition

Recent findings of the MESSENGER mission on Mercury have brought new evidence for its reducing nature, widespread volcanism and surface compositional heteregeneity. MESSENGER also provided major elemental ratios of its surface that can be used to infer large-scale differentiation processes and the thermal history of the planet. Mercury is known as being very reduced, with very low Fe-content and high S and alkali contents on its surface. Its bulk composition is therefore likely close to EH enstatite chondrites. In order to elucidate the origin of the chemical diversity of Mercury's surface, we determined the melting properties of EH enstatite chondrites, at pressures between 1 bar and 3 GPa and oxygen fugacity of IW-3 to IW-5, using piston-cylinder experiments, combined with a previous study on EH4 melting at 1 bar. We found that the presence of Ca-rich sulfide melts induces significant decrease of Ca-content in silicate melts at low pressure and low degree of melting (F). Also at pressures lower than 3 GPa, the SiO2-content decreases with F, while it increases at 3 GPa. This is likely due to the chemical composition of the bulk silicate which has a (Mg+Fe+Ca)/Si ratio very close to 1 and to the change from incongruent to congruent melting of enstatite. We then tested whether the various chemical compositions of Mercury's surface can result from mixing between two melting products of EH chondrites. We found that the majority of the geochemical provinces of Mercury's surface can be explained by mixing of two melts, with the exception of the High-Al plains that require an Al-rich source. Our findings indicate that Mercury's surface could have been produced by polybaric melting of a relatively primitive mantle.

Boujibar, A.↗

Spectral identification of chemisorbed CO2 and application to Mars analog materials

The goal of this work is to identify the spectral signature of chemisorbed CO2, to test the efficacy of carbonate formation on Mars-analog materials via CO2 chemisorption, and to identify the surface-chemical characteristics of good chemisorbents, with the intent of assessing the possible geochemical importance of CO2 chemisorption as a quasipermanent CO2 sink in the Martian environment. Our approach is to search for infrared spectral bands that result from chemisorption of CO2 molecules onto chemical reagents and Mars-analog materials, and to identify the salient differences in adsorbents that favor strong, permanent CO2 chemisorption. The total amount of CO2 in the early Martian atmosphere, and consequent surface temperatures, are unknown. A CO2 greenhouse may not have been an adequate mechanism under any circumstances; however, it if were, then most of that CO2 must still be in the near-surface environment; no escape mechanism that could remove it after the decline of channeling has been identified. The only plausible reservoir is carbonate, and there are various remote sensing techniques that can be used to search for it. We are investigating CO2 chemisorption as a permanent CO2 sink, and to aid in interpretation of remotely sensed IR spectra of Mars. A common effect reported in CO2 adsorption studies is the formation of a layer of carbonate or bicarbonate anions on adsorbents that have OH- groups available on their surfaces. Inorganic hydroxyls occur on phyllosilicates, amorphous silicates, metal oxides and hydroxides; it is the most abundant and reactive surface functional group on the surfaces of terrestrial silicates. The process responsible for the reaction is chemisorption. Chemisorption is distinguished from physical adsorption in that there is a transfer of electrons between species, and the formation of a chemical bond. The heat of chemisorption is typically of the same order as heats of chemical reaction (i.e., a few hundred to a few thousand kJ/mole), as opposed to heats of physical adsorption (a few kJ per mole). Chemisorption is an activated process that is promoted by an increase in temperature - quite the opposite of physical adsorption. Chemisorption is not reversible in the sense that physical adsorption is.

Zent, A. P.↗

Depositional facies and aqueous-solid geochemistry of travertine-depositing hot springs (Angel Terrace, Mammoth Hot Springs, Yellowstone National Park, U.S.A.)

Petrographic and geochemical analyses of travertine-depositing hot springs at Angel Terrace, Mammoth Hot Springs, Yellowstone National Park, have been used to define five depositional facies along the spring drainage system. Spring waters are expelled in the vent facies at 71 to 73 degrees C and precipitate mounded travertine composed of aragonite needle botryoids. The apron and channel facies (43-72 degrees C) is floored by hollow tubes composed of aragonite needle botryoids that encrust sulfide-oxidizing Aquificales bacteria. The travertine of the pond facies (30-62 degrees C) varies in composition from aragonite needle shrubs formed at higher temperatures to ridged networks of calcite and aragonite at lower temperatures. Calcite "ice sheets", calcified bubbles, and aggregates of aragonite needles ("fuzzy dumbbells") precipitate at the air-water interface and settle to pond floors. The proximal-slope facies (28-54 degrees C), which forms the margins of terracette pools, is composed of arcuate aragonite needle shrubs that create small microterracettes on the steep slope face. Finally, the distal-slope facies (28-30 degrees C) is composed of calcite spherules and calcite "feather" crystals. Despite the presence of abundant microbial mat communities and their observed role in providing substrates for mineralization, the compositions of spring-water and travertine predominantly reflect abiotic physical and chemical processes. Vigorous CO2 degassing causes a +2 unit increase in spring water pH, as well as Rayleigh-type covariations between the concentration of dissolved inorganic carbon and corresponding delta 13C. Travertine delta 13C and delta 18O are nearly equivalent to aragonite and calcite equilibrium values calculated from spring water in the higher-temperature (approximately 50-73 degrees C) depositional facies. Conversely, travertine precipitating in the lower-temperature (< approximately 50 degrees C) depositional facies exhibits delta 13C and delta 18O values that are as much as 4% less than predicted equilibrium values. This isotopic shift may record microbial respiration as well as downstream transport of travertine crystals. Despite the production of H2S and the abundance of sulfide oxidizing microbes, preliminary delta 34S data do not uniquely define the microbial metabolic pathways present in the spring system. This suggests that the high extent of CO2 degassing and large open-system solute reservoir in these thermal systems overwhelm biological controls on travertine crystal chemistry.

Non-NASA Center↗

Shocked quartz and more: Impact signatures in K-T boundary clays and claystones

Quartz grains displaying multiple sets of planar features are described from numerous Cretaceous-Tertiary (K-T) boundary clays and claystones at both marine and nonmarine depositional sites around the world. All these sites also show anomalously high amounts of iridium and enrichments of other siderophile elements in cosmic ratios within these boundary units. This combination of mineralogical and geochemical features are used in support of an impact hypothesis for the end-Cretaceous event. Recently, it was suggested that some combination of explosive and nonexplosive volcanism associated with the formation of the Deccan traps in India could be responsible for the mineralogy and geochemistry seen in the K-T boundary units. Besides the obvious contradition of simultaneous explosive and nonexplosive volcanism from one locality during an instant of geologic time, there remains the difficulty of spreading both iridium (and trace elements in cosmic proportions) and quartz grains around the world by volcanic (atmospheric) transport. In addition, the ability of volcanism to produce the type of shock metamorphism seen in minerals at the K-T boundary was not demonstrated. Multiple sets of shock lamellae in quartz are considered characteristic of shock metamorphism in rocks at the sites of known impact craters and are the type of deformation seen in quartz from K-T boundary clays and claystones. Single sets of poorly defined lamellae described from rare quartz grains in certain volcanic deposits are characteristic of tectonic deformation and do not correspond to the shock lamellae in quartz from K-T sediments and impact structures. So-called shock mosaicism in quartz and feldspar grains described from volcanic deposits can result from many processes other than shock metamorphism, and therefore is not considered to be an effect characteristic solely of shock. The mineralogy of shock-metamorphosed grains at the K-T boundary also argues against a volcanic origin.

Bohor, Bruce F.↗

Noctis Landing: A Proposed Landing Site/Exploration Zone for Human Missions to the Surface of Mars

The proposed Noctis Landing Site/Exploration Zone (LS/EZ) is shown in Figure 1. Our preliminary study suggests that the proposed site meets all key Science and Resources (incl. Civil Engineering) requirements. The site is of significant interest, as the EZ not only offers a large number and wide range of regions of interest (ROIs) for short-term exploration, it is also located strategically at the crossroads between Tharsis and Valles Marineris, which are key for long-term exploration. The proposed site contains Regions of Interest (ROIs) that meet the following Science requirements: -­‐ Access to (1) deposits with a high preservation potential for evidence of past habitability and fossil biosignatures and (2) sites that are promising for present habitability. The site presents a wide variety of ROIs qith likely aqueous features and deposits, including sinous channels and valleys, slope gullies, lobate debris aprons, impact craters with lobate ejecta flows, and "bathtub ring" deposits. Neutron spectrometry also suggests hydrogen is present within the topmost 0.3 m or so of 4 to 10 wt% WEH (Water Equivalent Hydrogen). -­‐ Noachian and/or Hesperian rocks in a stratigraphic context that have a high likelihood of containing trapped atmospheric gases. Collapsed canyon rim material with preserved stratigraphy is abundantly present and accessible. -­‐ Exposures of at least two crustal units that have regional or global extents, that are suitable for radiometric dating, and that have relative ages that sample a significant range of martian geological time. Canyons floors in Ius Chasma, Tithonium Chasma, and plateau tops on Tharsis and in Sinai Planum offer access to distinct crustal units of regional extent. -­‐ Access to outcrops with linked morphological and/or geochemical signatures indicative of aqueous or groundwater/ mineral interactions. Iron and sulfur-bearing deposits on canyon floors in Noctis Labyrinthus, and in Ius Chasma (IC) and Tithonium Chasma (TC) offer many such outcrop options. -­‐ Identifiable stratigraphic contacts and cross-cutting relationships from which relative ages can be determined. In place and collapsed canyon walls in NL, TC, and IC offer such opportunities. -­‐ Other types of ROIs include access points to surrounding plateau top areas for longer term regional exploration. A key attribute of the proposed Noctic Landing site is its strategic location to allow the shortest possible surface excusions to Tharsis and Valles Marineris (VM). VM is the feature and region on Mars that exposes the longest record of Mars' geology and evolution through time. Tharsis is the region of Mars that has experienced the longest and most extensive volcanic history, and might still be volcanically active. Some of the youngest lava flows on Mars have been identified on the western flanks of the Tharsis Bulge, i.e., within driving range of future longrange (500 - 1000 km) pressurized rover traverses. The proposed site also contains ROIs that offer the following Resources (incl. Civil Engineering) characteristics: -­‐ Access to raw material that exhibits the potential to (1) be used as feedstock for water-generating in situ resource utilization (ISRU) processes and (2) yield significant quantities (greater than 100 MT) of water. The raw material is likely in the form of hydrated minerals, and possibly ice/regolith mix. The top of the raw material deposit is at the surface. -­‐ Access to a region where infrastructure can be emplaced or constructed. This region is less than 5 km from the LS and contains flat, stable terrain. The region exhibits evidence for an abundant source of loose regolith. Several deep pits in the area combined with the availability of sand suggests that some natural terrain features can be adapted for construction purposes. -­‐ Access to raw material that exhibits the potential to be used as metal feedstock for ISRU and construction purposes. Iron and sulfur-rich mineral surface deposits have been identified in CRISM data in many locations in this area. Noctis Landing is the lowest-altitude location on Mars that straddles both the Tharsis region (above average geothermal gradients) and Valles Marineris (minimal crustal thickness from surface (valley floor) to a subsurface liquid water table. Noctis Landing has the potential for being an ideal site for eventual deep drilling on Mars to access deep subsurface liquid water and potentially encountering extant life. Available data remains insufficient to fully qualify the Noctis Landing site. Additional remote sensing data (visible, Near and Mid-IR, and radar) and surface reconnaissance via a high-mobility robotic rover are recommended. In particular, it will be important to assess the trafficability of the site, and its potential for yielding water and metals as a resource. Access to plateau tops from the Noctis Landing site on the canyon floor should be demonstrated. Future exploration of the site would also be enhanced significantly by the availability of robotic (tele-operatable) surveying and sample-collecting drones. Testing of the use of such collaborative science and exploration technologies should be conducted at terrestrial sites such as the Haughton-Mars Project site on Devon Island, High Arctic, among others. Note: Noctis Landing is not an official Mars nomenclature name for this location. Because the area of the proposed LS/EZ had no name, and because it is close to Noctis Labyrinthus to the West while being distinct from it, the provisional name Noctis Landing is proposed. Noctis means night in Latin.

Lee, Pascal↗

Targeted Rare Earth Element Extraction from Mine Drainage Treatment Solids Informed by Advanced Characterization

In support of a clean energy transition in the U.S., National Energy Technology Laboratory (NETL) has collaborated with staff at Hedin Environmental and students at the University of Pittsburgh to characterize critical mineral content and recovery potential from acid mine drainage treatment solids (AMD solids). AMD solids in Appalachia are an unconventional feedstock of rare earth elements (REEs), with potential of suppling 1,102 tons REE/year. To inform recovery efforts, select AMD solids were examined using synchrotron microprobe analysis in conjunction with USGS-developed geochemical modeling to indicate likely phases hosting critical minerals (REE, Co, Ni, etc.) and associated metals . More than 100 AMD solids were collected from 94 passive AMD treatment systems in Pennsylvania, where limestone aggregates are used for acidity neutralization. As pH increases, dissolved metals and critical minerals in AMD are attenuated as surface coatings on limestone. The collected AMD solids contained up to 2000 mg/kg REE, up to 13,000 mg/kg transition metals (Co, Ni, Zn) and up to 440 mg/kg Li. Regardless of the diverse chemical compositions from AMD solids (Al-rich, Mn-rich, or Al,Fe,Mn-rich), REEs were mostly associated with Al and Mn (hydr)oxides, while select heavy REEs (e.g., Gd, Dy) were co-localized with Fe (hydr)oxides. Co and Ni have different distribution zones, while both co-localized with Mn (hydr)oxides. Based on this characterization, NETL developed a patent-pending innovative step-leaching protocol, “Targeted Rare Earth Extraction (TREE)” to effectively recover up to 90% REE and 60% Co in separate steps. In addition, select post-TREE solid residuals (purified Al oxides, or Mn oxides) can be further developed into functional materials (e.g., lithium and CO2 sorbents) needed for green energy transition and carbon management. This characterization-informed approach as well as TREE processing from AMD solids can be used for other legacy wastes (e.g., coal ash, oil and gas drill cutting, mine tailings), and offers an opportunity to transform waste streams into environmental and economic assets that meet U.S. Department of Energy and U.S. Environmental Protection Agency goals.

characterization and extraction of rare earth elem↗

Steptoe Valley NV Data Compilation: Understanding a Stratigraphic Hydrothermal Resource through Geophysical Imaging

Sandia National Laboratories partnered with a multi-disciplinary group of subject matter experts to evaluate a stratigraphic geothermal resource in Steptoe Valley, Nevada using both established and novel geophysical imaging techniques. Provided here are a compilation of newly acquired data over the area and select modeling efforts. This encompasses a 3D geological model (inclusive of full Leapfrog files, Leapfrog viewer files, and XYZ data for faults and stratigraphy) with embedded geophysical modeling, controlled-source electromagnetic (CSEM) and magnetotelluric (MT) data packages, aqueous spring geochemistry data, seismic reflection interpretations, and a gravity data package. The stratigraphic reservoir in Steptoe Valley was previously discovered during oil and gas exploration. Subsequent studies, such as the Nevada Play Fairway Analysis, added data which further highlighted potential resource targets in the basin. Geophysical surveys, complimented with refined geologic mapping and geochemical sampling, were deployed to further characterize the resource. The resulting 3D geologic interpretation, conceptual model refinements, and reservoir simulations suggest that a power-capable reservoir is economically accessible in the Paleozoic carbonates of the deep/central basin. Additional geophysical characterization and exploration drilling efforts are recommended to calibrate interpretation and determine where/how to potentially develop the Steptoe resource. The geophysical tools, interpretations, lessons learned, and publicly available data generated by this study establish an exploration methodology to inform decisions for successful development of stratigraphic reservoirs.

15 GEOTHERMAL ENERGY↗

Novel Geochemistry Determined from High P-T Simulation Experiments of HFTS 2

A standard method in unconventional oil and gas production is the process of hydraulic fracturing followed by a shut-in period, during which the fracture fluid remains pressurized in the reservoir for up to three weeks before production begins. Despite this widely used process, very little is known about what occurs in the reservoir during this shut-in process. In order to properly delineate potential reservoir reactions that may occur during shut-in that would lead to corrosion and scaling events, experiments were conducted in high pressure, high temperature reactors to simulate conditions of the Wolfcamp Formation in the Delaware Basin. Experimental design allowed the assessment of the effect of proppant, microbiology, and time on the mineralogy and fluid chemistry in the reservoir. Results suggest the biggest impact on fluid chemistry and shale mineralogy during shut-in is time. Analyses demonstrate dissolution of the shale material, with maximum dissolved ions occurring after 7 days of the shut-in period. After 21 days, results suggest precipitation occurs. The Delaware Basin is demonstrated to be high in sulfate content, which further increases in the fluid due to dissolution reactions during shut-in. The pressure vessel experiments suggest there was no significant contribution to reactions from microbiology during the shut-in period. However, early production samples demonstrate a significant selection of the microorganism Caminicella, a genus of which has previously been correlated to corrosion and sulfide production. Results suggest shut-in conditions may provide high sulfate concentrations that could later be utilized by a shifted microbial community to drive potential well infrastructure failure. This is the first study to incorporate microbiology, mineralogy, and fluid chemistry to investigate the fundamental geochemical reactions that occur during shut-in and early phase production of the Delaware Basin. Results from this study can complement observations from the Hydraulic Fracture Test Site 2 observations.

Gulliver, Djuna↗

Simulating the Surface of Venus on Earth

The growing interest in comparative climatology among the terrestrial planets, the explosion of planets being discovered around other stars and the exciting results of recent orbital and remote observations of Venus provide evidence for a growing case to better understand Earths sister planet. The surface of Venus is quite unlike Earths surface conditions, and in fact is rather extreme. Science, technology, and planetary mission communities have a growing interest in the unique physiochemical properties and processes that occur under extreme temperature and pressure conditions in exotic and even hostile chemical environments such as Venus. The steadily growing catalog of exoplanets likely contains many examples of bodies with environments dramatically different than the surface of the Earth. Understanding these properties and processes will help us under-stand the history and present day state of inhospitable and even inaccessible regions of the Earth as well as other solar or extrasolar planets. Additionally, Venus and Saturn targets are prioritized in the current Planetary Decadal Survey, with reference missions that include in-situ investigations of these challenging environments. The fact that two of the five recent Discovery mission proposals selected by NASA for further development are Venus-focused adds additional priority and even urgency to laboratory-based extreme environment investigations. In addition to the importance of science-focused investigations, there is a current and future need for understanding the behavior of advanced technologies and materials in these extreme environments. The materials of course make up instruments and systems in missions and ultimately the success of planetary missions is dependent upon performance testing of instruments and systems in conditions that closely approximate those of the target. Until very recently, there was limited ability to accurately simulate Venus surface-like conditions, especially in vessels large enough to accommodate full-size instruments and components. This gap in capability is being addressed by NASA Glenn's Extreme Environment Rig, called GEER, located in Cleveland, Ohio. This large chamber allows for engineering tests of newly-developed as well as heritage instruments, while simultaneously affording opportunities for geochemical and materials-based science investigations.

Simulation↗

Energetics of hydroxylbastnäsite solid solutions, La 1-$\chi$ Nd $\chi$ CO 3 OH

Bastnäsites (LnCO 3 (F,OH)) are a group of common rare earth elements (REE)-bearing minerals and are one of the primary global sources of REE. Due to the chemical similarities among REE, bastnӓsites tend to occur as solid solutions instead of end members in REE containing ores. To better understand the processes and the mechanisms of formation of such deposits, it is essential to determine the thermodynamic properties of bastnӓsites, including hydroxylbastnӓsite (LnCO 3 OH) solid solutions. In this work, we performed detailed structural and calorimetric investigations on synthetic hexagonal La–Nd hydroxylbastnӓsite (La 1-$\chi$ NdCO 3 OH, $\chi$ = 0, 0.25, 0.5, 0.75, 1) solid solutions. X-ray diffraction confirms the crystal structure of the solid solution series in the $\ P$6 space group, and pair distribution function (PDF) analysis reveals local bonding environments characterized by three different types of 9-coordinated metal-oxygen polyhedra. Unit cell parameters of La1–xNdxCO3OH exhibit a nearly linear relation with the Nd content x, suggesting a random distribution of La and Nd in the structure. Their standard enthalpies of formation (Δ$\ H$° f ) were determined by high temperature oxide melt drop solution calorimetry, from which the enthalpies of mixing (Δ$\ H$ mix ) were derived. The Δ$\ H$ mix can be fitted by a regular solution model with an interaction parameter of 12.58 ± 0.16 kJ/mol, suggesting enthalpic metastability of La1–xNdxCO3OH relative to the two endmembers. Combining entropy and enthalpy, we further estimated the Gibbs free energies of mixing (Δ$\ G$ mix ) at relevant temperatures, revealing favorable temperatures under which the intermediate La 1-$\chi$ NdCO 3 OH phases can be stabilized. Such entropy-driven stabilization, as is consistent with our geochemical modeling results, may explain the enhancement of thermal stability of the solid solutions in nature. Additionally, the temperature range constrained from this study may be used to estimate the thermal history of REE bastnӓsite deposit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗