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All sourcesNASA NTRSDOE OSTI
NASA NTRS1995

NIMS - Callisto Science Objectives and Observational Plans

The Galileo Near Infrared Spectrometer (NIMS) provides a combination of spectroscopic and imaging capabilities. For geological studies of Callisto, this instrument can perform regional mapping while simultaneously determining composition and mineralogy. This data can help determine the surface evolution. NIMS will search for hydroxilated silicates, opaque minerals, and organic material.

Galileo Callisto near infrared spectrometer planet↗
NASA NTRS1995

Long-wavelength Radar Studies of the Lunar Maria

Radar measurements at 70 cm and 7.5 m wavelengths provide insight into the structure and chemical properties of the upper 5-100 m of the lunar regolith and crust. Past work has identified a number of anomalous regions and changes in echo strength, some attributed to differences in titanium content. There has been little opportunity, however, to compare calibrated long-wavelength backscatter among different units or to theoretical model results. We combine recent high-resolution (3-5 km) 70-cm radar data for the nearside with earlier calibrated full-disk observations to provide a reasonable estimate of the true lunar backscatter coefficient. These data are tested against models for quasi-specular scattering from the surface, echoes from a buried substrate, and Mie scattering from surface and buried rocks. We find that 70 cm echoes likely arise from Mie scattering by distributed rocks within the soil, consistent with earlier hypotheses. Returns from a buried substrate would provide a plausible fit to the observations only if the regolith depth were ~3 m or less and varied little across the maria. Depolarized echoes are due to some combination of single and multiple scattering events, but it appears that single scattering alone could account for the observed echo power, based on comparisons with terrestrial rocky surfaces. Backscatter strength from the regolith is most strongly affected by the loss tangent, whose variation with mineral content is still poorly defined. We compared the backscatter values for the mare deposits to the oxide contents inferred from spectral ratio methods, and found that in general the unit boundaries evident in radar images closely follow those seen in color difference images. The 70-cm data are not well correlated with TiO2 values found using the Charette relationship nor with Fe abundances derived from Clementine observations. The lack of a relationship between radar echo and Fe content is reasonable given the distribution of iron among various mineral phases, but ilmenite content (FeTiO3) has typically been cited as the dominant cause of changes in loss tangent (and thus the radar absorption). The lack of correlation between the radar data and TiO2 estimates may arise from uncertainties in the Charette technique, subtle differences in the upper surface and bulk properties of the regolith, mineralogic effects on the radar not linked to titanium content, or to some combination of these factors. Dark crater haloes in the mare and highlands, and low radar returns from apparent cryptomare regions, are used to illustrate the role radar data can play in identifying changes in regolith composition; low-return haloes around craters such as Petavius may indicate 5-25% contamination of the highlands soil by excavated mare material or a layer of rock-poor ejecta at least several meters deep. The 7.5-m data were shown to correlate to a reasonable degree with estimates of Fe abundance, suggesting that this component of the mare basalts is primarily responsible for attenuation losses at very long wavelengths. The different sensitivities of the two radar wavelengths and multispectral data offers the potential for future deep mapping of the mare lava flows and regolith.

Lunar MariaRadarLunar Studies↗
NASA NTRS1995

Long-wavelength Radar Studies of the Lunar Maria

Radar measurements at 70 cm and 7.5 m wavelengths provide insight into the structure and chemical properties of the upper 5-100 m of the lunar regolith and crust. Past work has identified a number of anomalous regions and changes in echo strength, some attributed to differences in titanium content. There has been little opportunity, however, to compare calibrated long-wavelength backscatter among different units or to theoretical model results. We combine recent high-resolution (3-5 km) 70-cm radar data for the nearside with earlier calibrated full-disk observations to provide a reasonable estimate of the true lunar backscatter coefficient. These data are tested against models for quasi-specular scattering from the surface, echoes from a buried substrate, and Mie scattering from surface and buried rocks. We find that 70 cm echoes likely arise from Mie scattering by distributed rocks within the soil, consistent with earlier hypotheses. Returns from a buried substrate would provide a plausible fit to the observations only if the regolith depth were approx.3 m or less and varied little across the maria. Depolarized echoes are due to some combination of single and multiple scattering events, but it appears that single scattering alone could account for the observed echo power, based on comparisons with terrestrial rocky surfaces. Backscatter strength from the regolith is most strongly affected by the loss tangent, whose variation with mineral content is still poorly defined. We compared the backscatter values for the mare deposits to the oxide contents inferred from spectral ratio methods, and found that in general the unit boundaries evident in radar images closely follow those seen in color difference images. The 70-cm data are not well correlated with TiO2 values found using the Charette relationship nor with Fe abundances derived from Clementine observations. The lack of a relationship between radar echo and Fe content is reasonable given the distribution of iron among various mineral phases, but ilmenite content (FeTiO3) has typically been cited as the dominant cause of changes in loss tangent (and thus the radar absorption). The lack of correlation between the radar data and TiO2 estimates may arise from uncertainties in the Charette technique, subtle differences in the upper surface and bulk properties of the regolith, mineralogic effects on the radar not linked to titanium content, or to some combination of these factors. Dark crater haloes in the mare and highlands, and low radar returns from apparent cryptomare regions, are used to illustrate the role radar data can play in identifying changes in regolith composition; low-return haloes around craters such as Petavius may indicate 5-25% contamination of the highlands soil by excavated mare material or a layer of rock-poor ejecta at least several meters deep. The 7.5-m data were shown to correlate to a reasonable degree with estimates of Fe abundance, suggesting that this component of the mare basalts is primarily responsible for attenuation losses at very long wavelengths. The different sensitivities of the two radar wavelengths and multispectral data offers the potential for future deep mapping of the mare lava flows and regolith.

Lunar Studies↗
NASA NTRS2014

The Near Earth Object Scout Spacecraft: A Low Cost Approach to in-situ Characterization of the NEO Population

In this paper we describe a micro/nano satellite spacecraft and a supporting mission profile and architecture designed to enable preliminary in-situ characterization of a significant number of Near Earth Objects (NEOs) at reasonable cost. The spacecraft will be referred to as the NEO Scout. NEO Scout spacecraft are to be placed in GTO, GEO, or cis-lunar space as secondary payloads on launch vehicles headed for GTO or beyond and will begin their mission after deployment from the launcher. A distinguishing key feature of the NEO scout system is to design the mission timeline and spacecraft to rendezvous with and land on the target NEOs during close approach to the Earth-Moon system using low-thrust/high- impulse propulsion systems. Mission feasibility and preliminary design analysis are presented along with detailed trajectory calculations. The use of micro/nano satellites in low-cost interplanetary exploration is attracting increasing attention and is the subject of several annual workshops and published design studies (1-4). The NEO population consists of those asteroids and short period comets orbiting the Sun with a perihelion of 1.3 astronomical units or less (5-8). As of July 30, 2013 10065 Near-Earth objects have been discovered. The spin rate, mass, density, surface physical (especially mechanical) properties, composition, and mineralogy of the vast majority of these objects are highly uncertain and the limited available telescopic remote sensing data imply a very diverse population (5-8). In-situ measurements by robotic spacecraft are urgently needed to provide the characterization data needed to support hardware and mission design for more ambitious human and robotic NEO operations. Large numbers of NEOs move into close proximity with the Earth-Moon system every year (9). The JPL Near-Earth Object Human Space Flight Accessible Targets Study (NHATS) (10) has produced detailed mission profile and delta V requirements for various NEO missions ranging from 30 to 420 days in duration and assuming chemical propulsion. Similar studies have been reported assuming high power electric propulsion for manned NEO rendezvous missions (11). The delta V requirement breakdown and mission profile data from references 10 and 11 are used as a basis for sizing the NEO Scout spacecraft and for conducting preliminary feasibility assessments using the Tsiokolvsky rocket equation, a (worst-case) delta V requirement of 10 km/sec, and a maximum spacecraft dry mass of 20 kg. Using chemical propellant for a 10 km/sec delta V drives spacecraft wet mass well above 300 kg so that chemical propulsion is a non-starter for the proposed mission profile and spacecraft wet mass limits. In contrast, a solar electric propulsion system needs only 8 kg of Xe propellant to accelerate the spacecraft to 10 km/sec in 163 days with 0.02 N of thrust and 500 W of power from1.6 sq m of 29% efficient solar panels. In a second example, accelerating a 4 kg payload to 7 km/sec over 180 days requires about 6.7 kg of propellant and 1.2 kg of solar panels (12 kg total spacecraft wet mass).

Koontz, Steven L.↗
NASA NTRS2016

Synthesis of Akaganeite in the Presence of Sulfate: Implications for Akaganeite Formation in Yellowknife Bay, Gale Crater, Mars

Akaganeite (beta-FeOOH) is an Fe(III) (hydr)oxide with a tunnel structure usually occupied by chloride. Akaganeite has been recently discovered in a mudstone on the surface of Mars by the Chemistry and Mineralogy (CheMin) and Sample Analysis at Mars (SAM) instruments onboard the Mars Science Laboratory (MSL) Curiosity Rover in Gale crater [1, 2]. Akaganeite was detected together with sulfate minerals [anhydrite (CaSO4) and basanite (2CaSO4·2H2O)] in the drilled Cumberland and John Clein mudstone samples at Yellowknife Bay [2]. Discovery of akaganeite and sulfates in the same samples suggests that sulfate ions could be present in aqueous solution during akaganeite formation. However, mechanism and aqueous environmental conditions of akaganeite formation (e.g., pH and range of sulfate concentration) in Yellowknife Bay remain unknown. The objective of our work was to perform synthesis of akaganeite without or with sulfate addition at variable pHs in order to constrain formation conditions of akaganeite in Yellowknife Bay, Gale crater on Mars.

Peretyazhko, T. S.↗
DOE OSTI2022

Impact of Concurrent Solubilization and Fines Migration on Fracture Aperture Growth in Shales during Acidized Brine Injection

Acidic hydraulic fracturing fluid chemically and physically alters shale rock fabric during injection and shut-in, creating a “reaction-altered zone” along the fracture faces. To better characterize the variable thickness and composition of this reaction-altered zone under advective flow, we take a coupled experimental and modeling approach. A fluidic cell, with six fiducial markers, is first fabricated to keep the rock sample in place during the core floods and to allow image alignment of acquired images. Then, we conduct a series of reactive core floods in a clay-rich siliceous Wolfcamp shale sample with 10 wt % carbonate, using a synthetic fracturing fluid under no confining stress and at room temperature. High-resolution computed tomography (CT) scans are periodically conducted to observe the spatial alteration of the fracture network. We then perform scanning electron microscopy (SEM-EDS) on the two orthogonal surfaces (fracture surface and freshly cut profile face) to generate high-resolution elemental maps that show the change in mineralogy, both with distance along a given flow path along a fracture surface and with depth from the fracture surface into the shale matrix. These results are contrasted against a two-dimensional (2D) advection-diffusion reaction model developed previously for batch reactions between shale and synthetic fracturing fluids. The model simulates the geochemical interaction occurring at the fracture/matrix interface and penetrating into the shale matrix during the reactive core flood. Both model and experimental results show that the acidic brine is neutralized during the core flood, corresponding to an increase in fracture aperture as a function of fluid volume injected with the greatest change near the inlet. SEM-EDS scans reveal significant dissolution of carbonates on the fracture surface without pyrite oxidation. The reactive transport model indicates that carbonate depletion into the shale interior should be observable, yet SEM-EDS shows no discernible loss of carbonate in the orthogonal profile face. The combination of these observations suggests an additional fracture evolution mechanism in the reactive system, i.e., fines migration. We show that fines migration enhances the access of fracturing fluid to the matrix resulting in a more pronounced fracture widening. Finally, we conclude that coupled mineral dissolution and fines migration govern fracture aperture growth during acidized brine injection. In this work, we effectively show the underlying risk of relying solely on models that do not include an important (transport) process that can alter the system significantly and propose a combined chemomechanical mechanism for fracture evolution appropriate for this shale mineralogy.

58 GEOSCIENCES↗
NASA NTRS2022

Ultraviolet Photooxidation of Smectite-Bound Fe(II) and Implications for the Origin of Martian Nontronites

Clay minerals detected with orbital and in situ instruments in ancient Martian terrains constrain Mars' climate and aqueous alteration history. Early in its history, Mars experienced an atmospheric redox change and iron-bearing clay minerals may preserve the effects of that transition. Ferrous smectites, the thermodynamically predicted product of chemical weathering of basalts under anoxic conditions, may have undergone oxidation by exposure to chemical oxidants in the atmosphere or regolith, or by direct photooxidation at the surface. To assess these potential oxidation pathways, ferrous trioctahedral smectites of varying initial iron content were synthesized and subjected to oxidation by ultraviolet (UV) irradiation. Experimental UV irradiation under an anoxic atmosphere equivalent to approximately 7 years of flux on the Martian surface caused partial oxidation of smectite-bound Fe (Fe3+/ΣFe = 16–18%) and octahedral sheet contraction. Metal-OH vibrational bands in visible/near infrared (VNIR) reflectance spectra of oxidized smectites changed in band depth and asymmetry with higher iron content. X-ray diffraction patterns of UV irradiated samples indicate the formation of a mixed di- and trioctahedral smectite or a secondary nontronite phase, possibly on the surfaces of higher iron content smectites. These experiments suggest that UV irradiation is able to oxidize structurally bound iron in smectites without the presence of other chemical oxidants. Photooxidation may have influenced the mineralogy, both syndepositionally and postdepositionally, of Martian alteration assemblages formed near the surface and this process needs not be limited to one part of their formation history. Plain Language Summary: Martian mineral assemblages observed with orbiters and rover instruments allow us to understand the planet's past climate and aqueous activity. Hydrated minerals that contain Fe(II) are of particular interest as they would have been affected by the early atmosphere becoming more oxidizing overtime, changing the structural iron into Fe(III). In this study, we synthesized Fe(II) smectites with varying iron content and irradiated them with an ultraviolet (UV) light source to test whether they could be photooxidized. Iron in the smectite minerals was incompletely oxidized by UV radiation after being exposed for the equivalent of approximately 7 years of exposure on the early Mars surface. The smectites with higher iron content showed more changes with photooxidation in their visible/near infrared spectra as well as in their X-ray diffraction patterns, two datasets collected by instruments on currently active Martian missions. These results suggest that UV photooxidation is a plausible contributor to the mineralogy and redox state of clay mineral assemblages observed at the Martian surface.

V. B. Rivera Banuchi↗
NASA NTRS1992

The fate of iron on Mars: Mechanism of oxidation of basaltic minerals to ferric-bearing assemblages

Perhaps the most conspicuous indication that chemical weathering has occurred on the surface of Mars is the overall color of the red planet and the spectroscopic features that identify ferric-bearing assemblages in the martian regolith. Apparently, Fe(2+) ions in primary minerals in parent igneous rocks on the martian surface have been oxidized to ferric iron, which occurs in degradation products that now constitute the regolith. The mineralogy of the unweathered igneous rocks prior to weathering on the martian surface is reasonably well constrained, mainly as a result of petrographic studies of the SNC meteorites. However, the alteration products resulting from oxidative weathering of these rocks are less well-constrained. The topics covered include the following: primary rocks subjected to chemical weathering; dissolution processes; oxidation of dissolved Fe(2+); mechanism of polymerization of hydrous ferric oxides; terrestrial occurrences of ferromagnesian smectites; and dehydroxylated Mg-Fe smectites on Mars.

Burns, Roger G.↗
NASA NTRS1993

The nanosphere iron mineral(s) in Mars soil

A series of surface-modified clays containing nanophase (np) iron/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these 'Mars-soil analogs' were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxyl mineral such as 'green rust', or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable meaghemite (gamma-Fe203) by mild heat treatment and then to nanophase hematite (aplha-Fe203) by extensive heat treatment. Their chemical reactivity offers a plausible mechanism for the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxide and silicate phase surfaces. The mode of formation of these (nanophase) iron oxides on Mars is still unknown.

Banin, A.↗
NASA NTRS1993

The nanophase iron mineral(s) in Mars soil

A series of surface-modified clays containing nanophase (np) iron oxide/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these "Mars-soil analogs" were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging, specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The clay acted as an effective matrix, both chemically and sterically, preventing the major part of the synthesized iron oxides from ripening, i.e., growing and developing larger crystals. The precipitated iron oxides appear as isodiametric or slightly elongated particles in the size range 1-10 nm, having large specific surface area. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxy mineral such as "green rust," or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable maghemite (gamma-Fe2O3) by mild heat treatment and then to nanophase hematite (alpha-Fe2O3) by extensive heat treatment. After mild heating, the iron-enriched clay became slightly magnetic, to the extent that it adheres to a hand-held magnet, as was observed with Mars soil. The chemical reactivity of the iron-enriched clays strongly resembles, and offers a plausible mechanism for, the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxides and silicate phase surfaces. The reflectance spectrum of the clay-iron preparations in the visible range is generally similar to the reflectance curves of bright regions on Mars. This strengthens the evidence for the predominance of nanophase iron oxides/oxyhydroxides in Mars soil. The mode of formation of these nanophase iron oxides on Mars is still unknown. It is puzzling that despite the long period of time since aqueous weathering took place on Mars, they have not developed from their transitory stage to well-crystallized end-members. The possibility is suggested that these phases represent a continuously on-going, extremely slow weathering process.

NASA Program Exobiology↗
NASA NTRS2015

Early Mars Climate Modeling and the Faint Young Sun Paradox.

Today Mars is a cold, dry, desert planet. Liquid water is not stable on its surface. There are no lakes, seas, or oceans, and precipitation falls as snowfall. Yet early in its history during the Noachian epoch, there is geological and mineralogical evidence that liquid water from rainfall flowed on its surface creating drainage systems, lakes, and - possibly - seas and oceans. More recent observations by Curiosity in Gale crater hint that such conditions may have persited into the Hesperian. The implication is that early Mars had a wamer climate than it does today as a result of a thicker atmosphere with a more powerful greenhouse effect capable of producing an active hydrological cycle with rainfall, runoff, and evaporation. Since Mariner 9 began accumulating such evidence, researchers have been trying to understand what kind of a climate system could have created greenhouse conditions favorable for liquid water. Unfortunately, the problem is not yet solved.

greenhouse gases↗
NASA NTRS2004

Initial results from the Mini-TES experiment in Gusev Crater from the Spirit Rover

The Miniature Thermal Emission Spectrometer (Mini-TES) on Spirit has studied the mineralogy and thermophysical properties at Gusev crater. Undisturbed soil spectra show evidence for minor carbonates and bound water. Rocks are olivinerich basalts with varying degrees of dust and other coatings. Dark-toned soils observed on disturbed surfaces may be derived from rocks and have derived mineralogy (+/-5 to 10%) of 45% pyroxene (20% Ca-rich pyroxene and 25% pigeonite), 40% sodic to intermediate plagioclase, and 15% olivine (forsterite 45% +/-5 to 10). Two spectrally distinct coatings are observed on rocks, a possible indicator of the interaction of water, rock, and airfall dust. Diurnal temperature data indicate particle sizes from 40 to 80 microm in hollows to approximately 0.5 to 3 mm in soils.

Minerals↗
NASA NTRS1988

Interactions of light with rough dielectric surfaces - Spectral reflectance and polarimetric properties

The nature of the interactions of visible and NIR radiation with the surfaces of rock and mineral samples was investigated by measuring the reflectance and the polarization properties of scattered and reflected light for slab samples of obsidian and fine-grained basalt, prepared to controlled surface roughness. It is shown that the degree to which radiation can penetrate a surface and then scatter back out, an essential criterion for mineralogic determinations based on reflectance spectra, depends not only upon the composition of the material, but also on its physical condition such as sample grain size and surface roughness. Comparison of the experimentally measured reflectance and polarization from smooth and rough slab materials with the predicted models indicates that single Fresnel reflections are responsible for the largest part of the reflected intensity resulting from interactions with the surfaces of dielectric materials; multiple Fresnel reflections are much less important for such surfaces.

Yon, S. A.↗
NASA NTRS2019

New Perspectives of Ancient Mars: Mineral Diversity and Crystal Chemistry at Gale Crater, Mars from the CheMin X-Ray Diffractometer

The Mars Science Laboratory Curiosity rover arrived at Mars in August 2012 with a primary goal of characterizing the habitability of ancient and modern environments. Curiosity landed in Gale crater to study a sequence of ~3.5 Ga old sedimentary rocks that, based on orbital visible/near-infrared reflectance spectra, contain secondary minerals that suggest deposition and/or alteration in liquid water. The sedimentary sequence that comprises the lower slopes of Mount Sharp within Gale crater may preserve a dramatic shift on early Mars from a relatively warm and wet climate to a cold and dry climate based on a transition from smectite-bearing strata to sulfate-bearing strata. The rover is equipped with cameras and geochemical and mineralogical instruments to examine the sedimentology and identify compositional changes within the stratigraphy. These observations provide information about variations in depositional and diagenetic environments over time. The Chemistry and Mineralogy (CheMin) instrument is one of two internal laboratories on Curiosity and includes a transmission X-ray diffractometer (XRD) and X-ray fluorescence (XRF) spectrometer with a Co-K source. CheMin measures loose sediment samples scooped from the surface and drilled rock powders. The XRD provides quantitative mineralogy of scooped and drilled samples to a detection limit of ~1 wt.%. Curiosity has traversed >20 km since landing and has primarily been exploring the site of a predominantly ancient lake environment fed by groundwater and streams emanating from the crater rim. Results from CheMin demonstrate an incredible diversity in the mineralogy of fluvio-lacustrine rocks that signify variations in source rock composition, sediment transport mechanisms, and depositional and diagenetic fluid chemistry. Abundant trioctahedral smectite and magnetite at the base of the section may have formed from low-salinity pore waters with a circumneutral pH within lake sediments. A transition to dioctahedral smectite, hematite, and Ca-sulfate going up section suggests a change to more saline and oxidative aqueous conditions within the lake waters themselves and/or within diagenetic fluids. The primary minerals detected in fluvio-lacustrine samples by CheMin also suggest diversity in the igneous source regions for the sediments, where abundant pyroxene and plagioclase in most samples suggest a basaltic protolith, but sanidine and pyroxene in one sample may have been sourced from a potassic trachyte, and tridymite and sanidine in another sample may have been transported from a rhyolitic source. Crystal chemistry of major phases in each sample have been calculated from refined unit-cell parameters, providing further constraints on aqueous alteration processes and igneous protoliths for the sediments. Perhaps one of the biggest mysteries revealed by the CheMin instrument is the high abundance of X-ray amorphous materials (15 to 73 wt.%) in all samples measured to date. X-ray amorphous materials were detected by CheMin based on the observation of broad humps in XRD patterns. How these materials formed, their composition, and why they persist near the martian surface remain a topic of debate. The sedimentology and composition of the rocks analyzed by Curiosity demonstrate that habitable environments persisted intermittently on the surface or in the subsurface of Gale crater for perhaps more than a billion years.

Rampe, E. B.↗
DOE OSTI2020

Engineered Barrier System R&D and International Collaborations – LANL (FY20): Spent Fuel and Waste Disposition

The United States Department of Energy’s Spent Fuel and Waste Disposition (SFWD) program is investigating the design and safety function of generic nuclear geologic repositories in a variety of geologic settings (salt, argillite, and crystalline rock). Different configurations and loadings of spent nuclear fuel and waste within disposal canisters are also being investigated, some of which have the potential to generate repository temperatures higher than previously considered (i.e., temperatures >100ºC) by foreign and domestic concepts. This report expands on engineered barrier material stability in a high temperature crystalline rock repository through high temperature hydrothermal experiments. Experiments were designed to develop engineered barrier system (EBS) concepts in a hightemperature crystalline environment in 1) bentonite-Grimsel Granodiorite interactions, 2) bentonite-cement reactions, and 3) interaction between waste canister materials and bentonite. Experiment results are applied to understanding long-term repository performance in terms of radionuclide isolation. One hydrothermal experiment was completed in the rocking autoclaves at LANL in FY-20: IEBS-6 (Grimsel Granodiorite + Wyoming bentonite + cured ordinary Portland cement + Grimsel Granodiorite synthetic groundwater, 250ºC/150 bar, 8 weeks). Several other experiments were planned but were delayed due to the COVID-19 pause in laboratory work. In addition, some characterization of the reaction products of experiments conducted in FY-20 was prevented by COVID-19. Mineral phase chemistry was not measured via electron microprobe analyses for IEBS-6. Quantitative X-ray diffraction results from IEBS-6 and HBT-1 were not completed. The missing analyses and discussion of the results will be included in next year’s report. New characterization that was completed includes scanning electron microscopy of reaction products from IEBS-6, quantitative X-ray diffraction results are presented from IEBS-1 through IBES-5, preliminary scanning electron microscope images and chemical analyses for IEBS-6, X-ray diffraction of the clay fraction from all experiments, measurement/imaging of mineral growth on the surface of steel coupons. Major observations pertaining to bentonite stability in a Grimsel Granodiorite environment include the stability of Na-montmorillonite at 250°C, the formation of trace CSH phases, and the formation of bentonite colloids on experiment cooling. The addition of a cured chip of Portland cement to the bentonite-Grimsel system results in slightly higher pH values and the formation of diverse secondary mineral phases that were not observed in the previous experiments (e.g., analcime, garronite, CSH phases). The new characterization efforts related to the interaction of stainless-steel coupons and bentonite clay focused on thickness and mineralogy of phases that formed at the steel surface. In Wyoming bentonite + Grimsel Granodiorite systems, newly formed minerals at the bentonitesteel coupon interface included alteration of the outermost steel edge to Fe,Cr-oxide phases, followed by Fe-rich phyllosilicates (Fe-saponite, chlorite) and interbedded Fe,Cr,Ni-sulfide phases (pentlandite). Hydrothermal experiments were completed to assess uranium-carbonate complexation at conditions relevant to high-temperature disposal. Autoclave solubility experiments were conducted at 150 to 250ºC with a range of carbonate and uranium concentrations. The experiment results were characterized via situ UV-Visible spectroscopy and synchrotron-based in situ XAS techniques. Results show a significant decrease in the stability of uranyl-carbonate complexes at temperatures above 100ºC along with the precipitation of uranium oxides. Further, at T > 200ºC, results show that uranyl-hydroxyl complexes control solubility of uranium instead of the previously predicted uranyl-carbonate species. These results are significant for understanding the mobility of uranium in the EBS, which will likely contain carbonate-rich fluids. International research efforts focused on three main areas: 1) participation in international conferences, 2) building collaborations with foreign repository programs, and 3) the initiation of an experimental program to complement the full-scale HotBENT test at the Grimsel test site. This experiment included Wyoming bentonite + low carbon steel + Grimsel Granodiorite synthetic groundwater and was run at the planned maximum temperature of the HotBENT test (200°C). Complete characterization of reaction products was hindered by disruptions to laboratory work but will be reported in the next FY. The experimental results obtained in FY-20 continue to document the wide-ranging effects of bulk composition and pressure-temperature conditions in the mineralogical and geochemical evolution of a high-temperature repository environment. Concepts developed will be used to inform models of long-term material stability in a generic crystalline rock-hosted repository.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1988

Asteroid and comet surfaces

Photometric and spectrophotometric studies of asteroids and comets are in progress to address questions about the mineralogical relationship between asteroids near the 3:1 Kirkwood gap and ordinary chondrite meteorites and between cometary nuclei and the surface of asteroids. Progress was made on a method to convert the measured excess UV flux in the spectrum of 2201 Oljato to column abundance of OH and CN. Spectral reflectance measurements of large asteroids near the 3:1 Kirkwood gap, which is expected to be the source of ordinary chondrite meteorites, were briefly examined and show no spectral signatures that are characteristic of ordinary chondrite meteorite powders measured in the lab.

Mcfadden, Lucy-Ann↗
NASA NTRS2003

The Miniaturized Moessbauer Spectrometer MIMOS II of the Athena Payload for the 2003 MER Missions

A first-order requirement of spacecraft missions that land on Mars is instrumentation for in situ mineralogical analysis. Moessbauer Spectroscopy is a powerful tool for quantitative analysis of Fe-bearing materials. The Athena Moessbauer spectrometer MIMOS II on the martian surface will provide: (1) identification of iron-bearing phases (e.g., oxides, silicates, sulfides, sulfates, and carbonates), (2) quantitative measurement of the distribution of iron among its oxidation states (e.g., Fe(2+)/Fe(3+) ratio), and (3) quantitative measurement of the distribution of iron among iron-bearing phases (e.g., the relative proportions of iron in olivine, pyroxene, and magnetite in a basalt) in rocks and soils. Moessbauer data will also be highly complementary with chemical analyses from the APXS and the Mini-TES compositional data. Mars is a particularly good place to do Moessbauer mineralogy because its surface is iron rich (approx. 20% Fe as Fe2O3). Moessbauer spectrometers that are built with backscatter measurement geometry require no sample preparation, a factor important for in situ planetary measurements.

G Klingelhoefer↗
NASA NTRS2011

The Regolith of 4 Vesta: Perspectives from Howardite Meteorites and Dawn Mission Observations

4 Vesta is the largest asteroid with a basaltic surface, the only surviving differentiated asteroid recording igneous processes from the earliest phase of solar system history. The Dawn spacecraft is in orbit about Vesta pursuing a campaign of high resolution imaging and visible and infrared spectrometry of the surface; compositional mapping by gamma-ray and neutron spectrometry will follow. Vesta is heavily cratered with a surface covered by impact debris, a regolith. One important goal of the Dawn mission is to develop an understanding of regolith processes that are affecting this surface debris. Regolith characteristics are a record of interaction with the environment (e.g., impactors, dust, solar wind, galactic cosmic-rays) and give evidence of surface processes (down-gravity movement, etc.). Regolith mineralogy and composition reflect the local bedrock, with influences from regional and global mixing. Understanding regolith processes will aid in determining the lithology of underlying crust. Vesta is most likely the parent asteroid of the howardite, eucrite and diogenite meteorites. Eucrites are intrusive and extrusive mafic rocks composed mostly of ferroan low-Ca clinopyroxene and calcic plagioclase, while diogenites are cumulate magnesian orthopyroxenites. Magmatism occurred within a few million years of the formation of the solar system and then ceased. Impacts into the igneous crust produced the howardites - polymict breccias composed of mineral and lithic debris derived mostly from eucrites and diogenites. Some howardites are true regolith breccias formed by lithification of extensively impact-gardened surface debris. However, howardites have a number of significant petrologic and compositional differences from mature lunar regolith breccias and soils reflecting the different environment around Vesta compared to that at 1 AU. The most significant differences are the higher impactor flux with a lower mean impact velocity and the lower gravity. As a result, regolith processes on Vesta differ in detail from those on the Moon. Laboratory study of howardites and orbital investigation of Vesta will allow for development of robust models of regolith formation on hand sample to multi-kilometer scales.

Mittlefehldt, David W.↗