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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
NASA NTRS1981

Use of thermal inertia determined by HCMM to predict nocturnal cold prone areas in Florida

Transparencies, prints, and computer compatible tapes of temperature differential and thermal inertia for the winter of 1978 to 1979 were obtained. Thermal inertial differences in the South Florida depicted include: drained organic soils of the Everglades agricultural area, undrained organic soils of the managed water conservation areas of the South Florida water management district, the urbanized area around Miami, Lake Okeechobee, and the mineral soil west of the Everglades agricultural area. The range of wetlands and uplands conditions within the Suwanee River basin was also identified. It is shown that the combination of wetlands uplands surface features of Florida yield a wide range of surface temperatures related to wetness of the surface features.

Allen, L. H., Jr.↗
NASA NTRS1988

Exploration of crustal/mantle material for the earth and moon using reflectance spectroscopy

Near-infrared reflectance spectra have been acquired (1) for Moses Rock diatreme in SE Utah using an airborne imaging spectrometer (AIS) and (2) for small areas in and around the large lunar impact crater Copernicus using a spectrometer on earth-based telescopes. The high spectral resolution and precision of these data allow several mineral components of surface material to be identified and analyzed in a spatial context. The derived mineralogical information is used to address specific geological problems. For the terrestrial study the distribution of the measured abundance of mantle derived ultramafic microbreccia across Moses Rock dike indicates that flow stabilized into a few channels during the violent eruption. For the lunar study the variety of rock types identified in crustal material of deep-seated origin is distinct from the dominant rock types sampled from the upper lunar crust and suggests a complex crustal evolution.

Pieters, Carle M.↗
NASA NTRS1994

Alendronate increases skeletal mass of growing rats during unloading by inhibiting resorption of calcified cartilage

Loss of bone mass during periods of skeletal unloading remains an important clinical problem. To determine the extent to which resorption contributes to the relative loss of bone during skeletal unloading of the growing rat and to explore potential means of preventing such bone loss, 0.1 mg P/kg alendronate was administered to rats before unloading of the hindquarters. Skeletal unloading markedly reduced the normal increase in tibial mass and calcium content during the 9 day period of observation, primarily by decreasing bone formation, although bone resorption was also modestly stimulated. Alendronate not only prevented the relative loss of skeletal mass during unloading but led to a dramatic increase in calcified tissue in the proximal tibia compared with the vehicle-treated unloaded or normally loaded controls. Bone formation, however, assessed both by tetracycline labeling and by [3H]proline and 45Ca incorporation, was suppressed by alendronate treatment and further decreased by skeletal unloading. Total osteoclast number increased in alendronate-treated animals, but values were similar to those in controls when corrected for the increased bone area. However, the osteoclasts had poorly developed brush borders and appeared not to engage the bone surface when examined at the ultrastructural level. We conclude that alendronate prevents the relative loss of mineralized tissue in growing rats subjected to skeletal unloading, but it does so primarily by inhibiting the resorption of the primary and secondary spongiosa, leading to altered bone modeling in the metaphysis.

NASA Discipline Musculoskeletal↗
NASA NTRS1978

Core 74001/2 - Grain size and petrology as a key to the rate of in-situ reworking and lateral transport on the lunar surface

A suite of samples from the double drive tube 74001/2 has been studied. Material from this core mainly consists of orange and black droplets interpreted to be volcanic pyroclastic ejecta. Grain size analysis indicates that this material is very homogeneous in its grain size properties. It is also the finest and best sorted suite of soil samples in the lunar collection having a mean grain size of 40 microns and a mean standard deviation of 1.75 phi. The upper 5.5 cm of this core has apparently undergone in situ reworking by meteorites over a period of about 10 million years. This reworked zone contains 'exotic' grains including basalt, mineral fragments, vitric breccias, and agglutinates. One type of agglutinate is unique and has been made primarily from orange and black glass droplets melted and welded together by micrometeorite impacts. Other agglutinates are made mainly from basaltic fragments and minerals. The amount of 'exotic' material added to the core combined with an estimate of the location of the source areas for the 'exotic' material allows us to estimate that a maximum of about 0.36 gm per sq cm of regolith surface is added from a radius of about 1 meter in 10 million years. Furthermore, no more than about 0.01 gm per sq cm of regolith surface is added from a radius of about 100 meters in 10 million years.

Mckay, D. S.↗
NASA NTRS2012

An Assessment of the Surface Longwave Direct Radiative Effect of Airborne Dust in Zhangye China During the Asian Monsoon Year Field Experiment (2008)

Tiny suspensions of solid particles or liquid droplets, called aerosols, hover in earth's atmosphere and can be found over just about anywhere including oceans, deserts, vegetated areas, and other global regions. Aerosols come in a variety of sizes, shapes, and compositions which depend on such factors as their origin and how long they have been in the atmosphere (i.e., their residence time). Some of the more common types of aerosols include mineral dust and sea salt which get lifted from the desert and ocean surfaces, respectively by mechanical forces such as strong winds. Depending on their size, aerosols will either fall out gravitationally, as in the case of larger particles, or will remain resident in the atmosphere where they can undergo further change through interactions with other aerosols and cloud particles. Not only do aerosols affect air quality where they pose a health risk, they can also perturb the distribution of radiation in the earth-atmosphere system which can inevitably lead to changes in our climate. One aerosol that has been in the forefront of many recent studies, particularly those examining its radiative effects, is mineral dust. The large spatial coverage of desert source regions and the fact that dust can radiatively interact with such a large part of the electromagnetic spectrum due to its range in particle size, makes it an important aerosol to study. Dust can directly scatter and absorb solar and infrared radiation which can subsequently alter the amount of radiation that would otherwise be present in the absence of dust at any level of the atmosphere like the surface. This is known as radiative forcing. At the surface dust can block incoming solar energy, however at infrared wavelengths, dust acts to partially compensate the solar losses. Evaluating the solar radiative effect of dust aerosols is relatively straightforward due in part to the relatively large signal-to-noise ratio in the measurements. At infrared wavelengths, on the other hand, the effect is rather difficult to ascertain since the measured dust signal level is on the same order as the instrumental uncertainties. Although the radiative impact of dust is much smaller in the infrared, it can still have a noticeable influence on the distribution of energy in the Earth-atmosphere system. This is mainly attributed to the strong light-absorptive properties commonly found in many earth minerals.

Hansell, Richard A.↗
DOE OSTI2024

Soil Organic Matter Dynamics in the Critical Zone

Soil is the thin, vital layer of Earth’s surface that forms the foundation of the Critical Zone and sustains life. This chapter explores the intricate dynamics of soil organic matter within the critical zone, focusing on three key thematic areas: deep soil organic matter, wildfire organic matter interactions, and organic matter erosion. Soil organic matter, although a small fraction of soil mass, plays a crucial role in soil function and ecosystem stability. The complexity of soil organic matter arises from its diverse chemical composition and interactions with minerals, which influence its persistence in the environment. This chapter begins by examining deep soil organic matter, which constitutes a significant portion of global carbon storage. We discuss how deep soil organic matter, typically isolated from surface processes, may become vulnerable to decomposition and carbon release due to disturbances. Next, we explore the impacts of fire on soil organic matter, particularly the formation and stability of pyrolyzed organic matter. The decomposition of pyrolyzer organic matter is influenced by its chemical composition and the surrounding environmental conditions, with implications for carbon cycling and soil fertility in post-fire ecosystems. Finally, the chapter addresses the role of erosion in soil organic matter dynamics. Erosion, accelerated by human activities, redistributes soil organic matter across landscapes, affecting its turnover and the broader biogeochemical cycles. We consider how micro-topographic features and erosion processes interact to influence soil OM stability and carbon sequestration. By synthesizing recent advances in these areas, this chapter provides a comprehensive overview of the complex and dynamic nature of soil organic matter in the critical zone, highlighting its importance in understanding the critical zone in the face of environmental change.

Moreland, Kimber↗
NASA NTRS2024

Characterization of NUW-LHT-5m, A Lunar Highland Simulant

A new simulant of the lunar highlands regolith, NUW-LHT-5M, was designed by NASA and manufactured by Washington Mills. The simulant was based on Apollo 16 data and is a member of the NU-LHT-series. NASA’s Marshall Space Flight Center and Johnson Space Center have already purchased 3 metric tons of the simulant for advanced engineering work. In support of engineering uses of the simulant, we provided measurements of the simulant including: mineral abundance and composition, liberation, X-ray fluorescence (XRF), ferrous iron, carbon, sulfur, 60 element inductively coupled plasma (ICP), loss on ignition, particle size, both 2D and 3D particle shape, specific surface area, shear, cohesion, internal friction, helium pycnometry, minimum index density, tap density, magnetic susceptibility, cryogenic and high temperature permittivity, visible and near-infrared (VNIR) and middle infra-red spectroscopy (MIR), differential scanning calorimetry (DSC), viscosity, thermal diffusivity, thermal conductivity, thermal gravimetric analysis (TGA), evolved gas analysis (EGA), and spark sintering. For the crystalline components the design of the simulant called for two rocks from the Stillwater Complex, Montana: 17.6 wt% norite, 37.7% anorthosite, and 4.7 wt% olivine from an unspecified commercial source. The other 40% of the simulant was a high calcium (An100), vesicular glass that Washington Mills made specifically for the simulant. Fabrication and quality control processes for both the glass and the simulant are described. Importantly, most of the graphs and tables presented herein provide values for both the new simulant and data for the older NASA mare simulant, JSC-1A. Finally, we discussed the current limitations of NUW-LT-5M and most other lunar regolith simulants to replicate the lunar material.

lunar regolith simulant↗
NASA NTRS1989

Soil developments in polar deserts: Implications for exobiology and future Mars missions

Chemical alterations, weathering, and diagenesis of soil profiles from the dry valleys of Antarctica were studied as analogs of regolith development for the Martian regolith. Chemical weathering processes play an important part in soil development within the dry valleys of Antarctica. A suite of core samples were studied which were taken within the valley floors in addition to samples taken in the vicinity of evaporite and brine ponds. Analysis of water soluable cations and anions from core samples were performed along with petrographic analysis of selected samples. It was shown that ionic transport processes operate primarily above the permafrost zone. Abundances of the water soluable ions reflect the nature of secondary minerals produced by evaporation and weathering. Chloride, calcium, and sodium abundances for soils from the cores within the North and South Forks of Wright Valley, reflect the secondary mineralogy of the soil columns. Calculations for Na, Ca, and Cl abundances reflect the appearance of halite and antarcticite. In areas where excess Ca is present, X-ray diffraction studies show the presence of gypsum. It is well known that the Martian surface conditions may be favorable for chemical weathering. Primary silicates would be expected to be reactive with any ground water. It seems likely that Martian subsurface water is available to assist in the weathering of the primary minerals. Such weathering could result in the formation of clays, sulfates, carbonates, hydrates, halides, and zeolites. The dry valley cores have shown that they maybe excellent analogs to weathering processes on the near-surface of Mars. Since movement of water within the near-surface region clearly results in chemical weathering, leaching, and salt formation in the dry valleys, similar processes are probably operating within the Martian regolith.

Gibson, Everett K., Jr.↗
DOE OSTI2021

Binding mechanism and binding free energy of amino acids and citrate to hydroxyapatite surfaces as a function of crystallographic facet, pH, and electrolytes

Hydroxyapatite (HAP) is the major mineral phase in bone and teeth. The interaction of individual amino acids and citrate ions with different crystallographic HAP surfaces has remained uncertain for decades, creating a knowledge gap to rationally design interactions with peptides, proteins, and drugs. In this contribution, we quantify the binding mechanisms and binding free energies of the 20 end-capped natural amino acids and citrate ions on the basal (001) and prismatic (010)/(020) planes of hydroxyapatite at pH values of 7 and 5 for the first time at the molecular scale. We utilized over 1500 steered molecular dynamics simulations with highly accurate potentials that reproduce surface and hydration energies of (hkl) hydroxyapatite surfaces at different pH values. Charged residues demonstrate a much higher affinity to HAP than charge-neutral species due to the formation of superficial ion pairs and ease of penetration into layers of water molecules on the mineral surface. Binding free energies range from 0 to -60 kJ/mol and were determined with ~10% uncertainty. The highest affinity was found for citrate, followed by Asp(-) and Glu(-), and followed after a gap by Arg(+), Lys(+), as well as by His(+) at pH 5. The (hkl)-specific area density of calcium ions, the protonation state of phosphate ions, and subsurface directional order of the ions in HAP lead to surface-specific binding patterns. Amino acids without ionic side groups exhibit weak binding, between -3 and 0 kJ/mol, due to difficulties to penetrate the first layer of water molecules on the apatite surfaces. We explain recognition processes that remained elusive in experiments, in prior simulations, discuss agreement with available data, and reconcile conflicting interpretations. In conclusion, the findings can serve as useful input for the design of peptides, proteins, and drug molecules for the modification of bone and teeth-related materials, as well as control of apatite mineralization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2011

Eucrite Impact Melt NWA 5218 - Evidence for a Large Crater on Vesta

Northwest Africa (NWA) 5218 is a 76 g achondrite that is classified as a eucrite [1]. However, an initial classification [2] describes it as a "eucrite shock-melt breccia...(in which) large, partially melted cumulate basalt clasts are set in a shock melt flow...". We explore the petrology of this clast-bearing impact melt rock (Fig. 1), which could be a characteristic lithology at large impact craters on asteroid Vesta [3]. Methods: Optical microscopy, scanning electronmicroscopy, and Raman spectroscopy were used on a thin section (Fig. 1) for petrographic characterization. The impact melt composition was determined by 20 m diameter defocused-beam analyses with a Cameca SX-100 electron microprobe. The data from 97 spots were corrected for mineral density effects [4]. Constituent mineral phases were analyzed with a focusedbeam. Bidirectonal visible and near-infrared (VNIR) and biconical FT-IR reflectance spectra were measured on the surface of a sample slab on its central melt area and on an eucrite clast, and from 125-500 m and <125 m powders of melt. Results: General petrography: The sample specimen is a coherent, medium dark-grey (N4), melt rock. The thin section captures a central, subophitic-textured melt that contains ~1 cm to tens of m-size subangular to rounded, variably-shocked eucrite clasts. Clasts >100 m are coarse-grained with equigranular ~1 mm size plagioclase, quartz, and clinopyroxene (Fig. 1). Single crystals of chromite, ilmenite, zircon, Ca-Mg phosphate, Fe-metal, and troilite are embedded in the melt. Polymineralic clasts are mostly compositionally similar to the above mentioned larger clasts but scarce granulitic fragments are observed as well.

Wittmann, Axel↗
DOE OSTI2020

Acid Erosion of Carbonate Fractures and Accessibility of Arsenic-Bearing Minerals: In Operando Synchrotron-Based Microfluidic Experiment

Underground flows of acidic fluids through fractured rock can create new porosity and increase accessibility to hazardous trace elements such as arsenic. In this study, we developed a custom microfluidic cell for an in operando synchrotron experiment using X-ray attenuation. The experiment mimics reactive fracture flow by passing an acidic fluid over a surface of mineralogically heterogeneous rock from the Eagle Ford shale. Over 48 h, calcite was preferentially dissolved, forming an altered layer 200–500 μm thick with a porosity of 63–68% and surface area >10$\times$ higher than that in the unreacted shale as shown by xCT analyses. Calcite dissolution rate quantified from the attenuation data was 3 $\times$ 10 –4 mol/m 2 s and decreased to 3 $\times$ 10 –5 mol/m 2 s after 24 h because of increasing diffusion limitations. Erosion of the fracture surface increased access to iron-rich minerals, thereby increasing access to toxic metals such as arsenic. Quantification using XRF and XANES microspectroscopy indicated up to 0.5 wt % of As(-I) in arsenopyrite and 1.2 wt % of As(V) associated with ferrihydrite. This study provides valuable contributions for understanding and predicting fracture alteration and changes to the mobilization potential of hazardous metals and metalloids.

58 GEOSCIENCES↗
NASA NTRS1993

Production of Ultrafine, High-purity Ceramic Powders Using the US Bureau of Mines Developed Turbomill

Turbomilling, an innovative grinding technology developed by the U.S. Bureau of Mines in the early 1960's for delaminating filler-grade kaolinitic clays, has been expanded into the areas of particle size reduction, material mixing, and process reaction kinetics. The turbomill, originally called an attrition grinder, has been used for particle size reduction of many minerals, including natural and synthetic mica, pyrophyllite, talc, and marble. In recent years, an all-polymer version of the turbomill has been used to produce ultrafine, high-purity, advanced ceramic powders such as SiC, Si3N4, TiB2, and ZrO2. In addition to particle size reduction, the turbomill has been used to produce intimate mixtures of high surface area powders and whiskers. Raw materials, TiN, AlN, and Al2O3, used to produce a titanium nitride/aluminum oxynitride (TiN/AlON) composite, were mixed in the turbomill, resulting in strength increases over samples prepared by dry ball milling. Using the turbomill as a leach vessel, it was found that 90.4 pct of the copper was extracted from the chalcopyrite during a 4-hour leach test in ferric sulfate versus conventional processing which involves either roasting of the ore for Cu recovery or leaching of the ore for several days.

Hoyer, Jesse L.↗
NASA NTRS1981

Time variability of Martian bolometric albedo

A time series of calibrated bolometric albedo maps of Mars is presented which establish accurate values of surface bolometric albedo and demonstrate changes in the bolometric appearance of specific regions with time of year and atmospheric conditions. The maps were constructed from Viking infrared thermal mapping data and provide global coverage at latitudes between -60 and +60 deg at 1 x 1 deg spatial resolution for a period spanning a Martian year and including the global dust storms of 1977. During dust-free periods, the bolometric albedo maps are found to be similar to classical earth-based visual albedo maps. A distinctly bimodal distribution of bolometric surface albedos is obtained even during the dust storms, with typical Lambert albedos of 0.27 and 0.16 for the bright and dark Martian surfaces, respectively. Atmospheric effects including dust storms are found to influence strongly apparent surface albedos, especially for dark areas, while neither bright nor dark regions show measurable long-term variations of bolometric albedo during clear periods.

Pleskot, L. K.↗
NASA NTRS2018

Ecosystem Carbon Emissions from 2015 Forest Fires in Interior Alaska

In the summer of 2015, hundreds of wildfires burned across the state of Alaska, and consumed more than 1.6 million ha of boreal forest and wetlands in the Yukon-Koyukuk region. Mapping of 113 large wildfires using Landsat satellite images from before and after 2015 indicated that nearly 60% of this area was burned at moderate-to-high severity levels. Field measurements near the town of Tanana on the Yukon River were carried out in July of 2017 in both unburned and 2015 burned forested areas (nearly adjacent to one-another) to visually verify locations of different Landsat burn severity classes (low, moderate, or high). Results: Field measurements indicated that the loss of surface organic layers in boreal ecosystem fires is a major factor determining post-fire soil temperature changes, depth of thawing, and carbon losses from the mineral topsoil layer. Measurements in forest sites showed that soil temperature profiles to 30 cm depth at burned forest sites increased by an average of 8o - 10o C compared to unburned forest sites. Sampling and laboratory analysis indicated a 65% reduction in soil carbon content and a 58% reduction in soil nitrogen content in severely burned sample sites compared to soil mineral samples from nearby unburned spruce forests. Conclusions: Combined with nearly unprecedented forest areas severely burned in the Interior region of Alaska in 2015, total ecosystem fire emission of carbon to the atmosphere exceeded most previous estimates for the state.

Ecosystem↗
DOE OSTI2022

Fundamental Studies on the Recovery of Rare Earth Elements from Coal and Coal Byproducts (Final Product Report)

The objective of this project was to collect fundamental information that can be used to develop disruptive physical and chemical separation methods that may be used to extract the rare earth elements (REEs) from coal-based feedstocks in a highly efficient, cost-effective, and environmentally benign manner. To meet the stated objective, a set of interrelated fundamental studies have been conducted. The project has been subdivided into three broad areas of tasks as follows, (1) measurement of surface forces in the thin liquid films (TLFs) of water confined between two macroscopic surfaces to establish the optimal conditions for efficiently collecting the ultrafine particles of rare earth minerals (REMs) present in the coal-based feedstocks using the flotation and/or the hydrophobic-hydrophilic separation process(es), (2) identification of the fundamental mechanisms by which REE ions adsorb and desorb on clay minerals present in coal byproducts, and the characterization of the ion-adsorption clays (IACs) present in U.S. coals, and (3) developing methods of extracting the REEs from the REMs and IACs present in US coal byproducts in a cost-effective and sustainable manner.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS2023

In Situ Chemical Reduction Interim Measures Work Plan Hot Spot 3 Mobile Launcher Platform Rehabilitation Sites / Vehicle Assembly Building Area (SWMU 056) Kennedy Space Center, Florida

This document presents the design details of an In Situ Chemical Reduction (ISCR) Interim Measures Work Plan for Hot Spot 3 within Mobile Launcher Platform Rehabilitation Sites/Vehicle Assembly Building Area, Solid Waste Management Unit (SWMU) 056 (SWMU 056), located at the John F. Kennedy Space Center, Florida. The interim measures (IM) treatment zone encompasses an area identified as the High Concentration Plume (HCP), which is defined as the area with chlorinated volatile organic compound (CVOC) groundwater concentrations greater than their respective Natural Attenuation Default Concentration (NADC). The objective of the IM is to remove CVOC mass within the treatment area to levels that facilitate a transition to natural attenuation monitoring. The IM design consists of the selected ISCR amendment, Provect-IR, which is a mixture of solid reagents in a single product that promotes enhanced reductive dechlorination and ISCR. ProvectIR includes natural antimethanogenic compounds; multiple hydrophilic, nutrient-rich organic carbon sources; zero valent iron; chemical oxygen scavengers; and vitamin and mineral sources. The proposed treatment area for this IM encompasses less than 1 acre and includes three vertical treatment intervals to reach the NADC plumes that vary per CVOC and depth: 4 to 10 feet below land surface (bls), 10 to 18 feet bls, and 42 to 52 feet bls. The amendment will be distributed through 16 injection points (IP01 through IP16) using dosing rates ranging from 0.4% to 0.6% of soil mass within the treatment interval and a 15% or 20% slurry strength. Dosage rates and slurry strength are based on groundwater geochemistry, soil characteristics, and contaminant concentrations. To aid in the evaluation of the ISCR IM performance, six performance monitoring wells will be installed following injections and sampled semiannually. CVOC parameters will be sampled until concentrations reduce to below their NADC. Underground Injection Control parameters will be sampled until concentrations decrease to background levels or to levels that meet respective groundwater standards. Sampling frequency will be evaluated annually and modified as needed. The path forward for the ISCR IM implementation includes preparing the IM Implementation Work Plan, ISCR injections, monitoring well installation, performance monitoring, and reporting.

Randall K. Sillan↗
NASA NTRS1998

The Stratigraphy and Evolution of the Lunar Crust

Reconstruction of stratigraphic relationships in the ancient lunar crust has proved to be a formidable task. The intense bombardment during the first 700 m.y. of lunar history has severely perturbed the original stratigraphy and destroyed the primary textures of all but a few nonmare rocks. However, a knowledge of the crustal stratigraphy as it existed prior to the cataclysmic bombardment about 3.9 Ga is essential to test the major models proposed for crustal origin, i.e., crystal fractionation in a global magmasphere or serial magmatism in a large number of smaller bodies. Despite the large difference in scale implicit in these two models, both require an efficient separation of plagioclase and mafic minerals to form the anorthositic crust and the mafic mantle. Despite the havoc wreaked by the large body impactors, these same impact processes have brought to the lunar surface crystalline samples derived from at least the upper half of the lunar crust, thereby providing an opportunity to reconstruct the stratigraphy in areas sampled by the Apollo missions. As noted, ejecta from the large multiring basins are dominantly, or even exclusively, of crustal origin. Given the most recent determinations of crustal thicknesses, this implies an upper limit to the depth of excavation of about 60 km. Of all the lunar samples studied, a small set has been recognized as "pristine", and within this pristine group, a small fraction have retained some vestiges of primary features formed during the earliest stages of crystallization or recrystallization prior to 4.0 Ga. We have examined a number of these samples that have retained some record of primary crystallization to deduce thermal histories from an analysis of structural, textural, and compositional features in minerals from these samples. Specifically, by quantitative modeling of (1) the growth rate and development of compositional profiles of exsolution lamellae in pyroxenes and (2) the rate of Fe-Mg ordering in orthopyroxenes, we can constrain the cooling rates of appropriate lunar samples. These cooling rates are used to compute depths of burial at the time of crystallization, which enable us to reconstruct parts of the crustal stratigraphy as it existed during the earliest stages of lunar history.

McCallum, I. Stewart↗
DOE OSTI2024

Silicate coprecipitation reduces green rust crystal size and limits dissolution-precipitation during air oxidation

Green rusts (GR) are mixed-valence iron (Fe) hydroxides which form in reducing redox environments like riparian and wetland soils and shallow groundwater. In these environments, silicon (Si) can influence Fe oxides’ chemical and physical properties but its role in GR formation and subsequent oxidative transformation have not been studied starting at initial nucleation. Green rust sulfate [GR(SO 4 )] and green rust carbonate [GR(CO 3 )] were both coprecipitated from salts by base titration in increasing % mol Si (0, 1, 10, and 50). The minerals were characterized before and after rapid (24 h) aqueous air-oxidation by x-ray diffraction (XRD), scanning electron microscopy (SEM), Fe extended x-ray absorption fine structure spectroscopy (EXAFS), and N 2 -BET surface area. Results showed that only GR(SO4) or GR(CO3) was formed at every tested Si concentration. Increasing % mol Si caused decreased plate size and increased surface area in GR(CO3) but not GR(SO4). GR plate basal thickness was not changed at any condition indicating a lack of Si interlayering. Air oxidation of GR(SO4) at all % mol Si contents transformed by dissolution and reprecipitation into lepidocrocite and goethite, favoring ferrihydrite with higher % Si content. Air oxidation of GR(CO3) transformed into magnetite and goethite but increasing Si caused GR to oxidize while retaining its hexagonal plate structure via solid-state oxidation. Our results indicate that Si has the potential to cause GR to form in smaller particles and upon air oxidation, Si can either stabilize the plate structure or alter transformation to ferrihydrite.

36 MATERIALS SCIENCE↗