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NASA NTRS1977

Dynamic crystallization experiments bearing on the origin of textures in impact-generated liquids

Dynamic crystallization experiments on a synthetic glass of 14310 composition show that the density and distribution of crystals present at the initiation of cooling can drastically affect the texture of the crystallized product. Experiments were performed in one-atmosphere gas-mixing furnaces at an oxygen fugacity slightly below iron-wustite, and precooling crystallization, cooling history, and melt history were systematically varied. When cooled from a complete liquid, the experimental charges were porphyritic with 1-2 mm phenocrysts set in a very fine-grained matrix (less than 0.1 mm). This result suggests that 14310 did not cool from a complete melt. When cooled from a crystal-liquid mixture, the experimental charges had widely varying textures depending on the density and distribution of crystals that act as nucleation sites. It is suggested that the close spatial association of widely divergent textures in the matrices of some breccias and rocks might arise in this manner; local variations in cooling rates are not required.

Lofgren, G. E.↗

NASA NTRS2010

Super Resolution Image Enhancement for a Flash Lidar: Back Projection Method

In this paper a new image processing technique for flash LIDAR data is presented as a potential tool to enable safe and precise spacecraft landings in future robotic or crewed lunar and planetary missions. Flash LIDARs can generate, in real-time, range data that can be interpreted as a 3-dimensional (3-D) image and transformed into a corresponding digital elevation map (DEM). The NASA Autonomous Landing and Hazard Avoidance (ALHAT) project is capitalizing on this new technology by developing, testing and analyzing flash LIDARs to detect hazardous terrain features such as craters, rocks, and slopes during the descent phase of spacecraft landings. Using a flash LIDAR for this application looks very promising, however through theoretical and simulation analysis the ALHAT team has determined that a single frame, or mosaic, of flash LIDAR data may not be sufficient to build a landing site DEM with acceptable spatial resolution, precision, size, or for a mosaic, in time, to meet current system requirements. One way to overcome this potential limitation is by enhancing the flash LIDAR output images. We propose a new super-resolution algorithm applicable to flash LIDAR range data that will create a DEM with sufficient accuracy, precision and size to meet current ALHAT requirements. The performance of our super-resolution algorithm is analyzed by processing data generated during a series of simulation runs by a high fidelity model of a flash LIDAR imaging a high resolution synthetic lunar elevation map. The flash LIDAR model is attached to a simulated spacecraft by a gimbal that points the LIDAR to a target landing site. For each simulation run, a sequence of flash LIDAR frames is recorded and processed as the spacecraft descends toward the landing site. Each run has a different trajectory profile with varying LIDAR look angles of the terrain. We process the output LIDAR frames using our SR algorithm and the results show that the achieved level of accuracy and precision of the SR generated landing site DEM is more than adequate for detecting hazardous terrain features and identifying safe areas.

Bulyshev, Alexander↗

NASA NTRS1991

Experimental reduction of simulated lunar glass by carbon and hydrogen and implications for lunar base oxygen production

The most abundant element in lunar rocks and soils is oxygen which makes up approximately 45 percent by weight of the typical lunar samples returned during the Apollo missions. This oxygen is not present as a gas but is tightly bound to other elements in mineral or glass. When people return to the Moon to explore and live, the extraction of this oxygen at a lunar outpost may be a major goal during the early years of operation. Among the most studied processes for oxygen extraction is the reduction of ilmenite by hydrogen gas to form metallic iron, titanium oxide, and oxygen. A related process is proposed which overcomes some of the disadvantages of ilmenite reduction. It is proposed that oxygen can be extracted by direct reduction of native lunar pyroclactic glass using either carbon, carbon monoxide, or hydrogen. In order to evaluate the feasibility of this proposed process a series of experiments on synthetic lunar glass are presented. The results and a discussion of the experiments are presented.

Mckay, David S.↗

NASA NTRS1973

Elastic wave velocities in anorthosite and anorthositic gabbros from Apollo 15 and 16 landing sites

Laboratory measurements of ultrasonic velocities in lunar samples 15065, 15555, 15415, 60015, and 61016 as well as in synthetic materials corresponding to compositions of anorthositic gabbros are presented as a function of hydrostatic pressure to about 7 kb. The author examined the seismic velocity distributions in the moon with reference to the variations to be expected in a homogeneous medium. The lunar mantle begins about 60 km, and the velocity of P waves in this area is about 7.7 km/sec. Variation of the seismic parameter with depth in the upper crust (about 20 km thick) is much too rapid to be explained by compression of a uniform material and the departure from expectation is so great that no reasonable adjustment of the material parameters can bring agreement; therefore, this author concludes that this result in this region of the moon is not due to self-compression but to textural gradients. In the lower crust (about 40 km thick), the region is shown to be relatively homogeneous, consisting probably of anorthositic rocks.

Chung, D. H.↗

NASA NTRS1985

Age-dating volcanic and alluvial surfaces with multipolarization data

A false-color multipolarization version of one of the images of Owens Valley area acquired by the JPL Synthetic Aperture Radar (SAR) is given. A geologic map of the alluvial fans there (Gillespie, 1982) is also given for comparison. In general, brightness in the multipolarization images can be seen to be inversely proportional to the age of the surfaces. A more detailed investigation of the relationship between backscatter and age of the surfaces was undertaken with calibrated aircraft SAR data. The quantitative relationship between backscatter coefficient and age for the three polarizations is shown. The straight lines connecting the measured data points imply a steady-state process, although the process or processes leading to this relationship may have operated at rates that varied with climate fluctuations, such as the glacial ages. It is expected that the relationship between radar brightness and age is a consistent one, and that with the wider availability of calibrated radar backscatter data, these relationships can be less well-known areas. The effect of variable such as past climate fluctuations, tectonic disturbance, and rock type must be understood before extension beyond the Mojave Desert region can be attempted.

Farr, T. G.↗

NASA NTRS2021

Carolina Coastal Plain Ecological Forecasting: Utilizing NASA Earth Observations to Map Suitable Venus Flytrap Habitat in an Effort to Inform Conservation, Seed Banking, and Reintroduction in the Carolina Coastal Plain and Sandhills Regions

Although the carnivorous plant Venus flytrap (Dionaea muscipula) is recognized globally, its native range is restricted to a small portion of the North and South Carolina Coastal Plain and Sandhills. Within this limited range, Venus flytrap populations are threatened by habitat loss, fire suppression, and poaching. NASA DEVELOP partnered with the North Carolina Botanical Garden (NCBG), the University of North Carolina Herbarium (NCU), and the North Carolina Natural Heritage Program (NCNHP) to support Venus flytrap conservation. The team developed models based on species presence data and environmental variables using the Software for Assisted Habitat Modeling (SAHM) to create a 2021 habitat suitability map for Venus flytrap. These models incorporated Earth observations collected by Landsat 8 Thermal Infrared Sensor (TIRS), Terra Moderate Resolution Imaging Spectroradiometer (MODIS), Advanced Land Observation Satellite (ALOS) Phased Array type L-band Synthetic Aperture Radar (PALSAR), and Sentinel-2 Multispectral Instrument (MSI). To predict areas at high risk of development, the team produced a 2050 land-use change map using TerrSet Land Change Modeler. The team found potential areas of conflict between predicted habitat and forecasted future development. Many areas of suitable habitat were concentrated along the coast where development was likely to occur, placing populations there at risk of extirpation. Overlaying suitable habitat with forecasted land change also identified suitable habitats with minimal risk of development, which may serve as lasting Venus flytrap habitat. These results can inform the NCBG and NCNHP’s conservation decision-making, including targeted seed banking, reintroduction, and prioritization of enduring habitats for protection and management.

Monika Rock↗

NASA NTRS2022

Carolina Coastal Plain Ecological Forecasting

Monika Rock↗

NASA NTRS2002

Russian-US Partnership to Study the 23-km-diameter El'gygtgyn Impact Crater, Northeast Russia

El'gygytgyn crater, located within Eastern Siberia, is a Pliocene-aged (3.6 Ma), well-preserved impact crater with a rim diameter of roughly 23 km. The target rocks are a coherent assemblage of crystalline rocks ranging from andesite to basalt. At the time of impact the region was forested and the Arctic Ocean was nearly ice-free. A 15-km lake fills the center of the feature and water depths are approximately 175 m. Evidence of shock metamorphism, -- including coesite, fused mineral glasses, and planar deformation features in quartz -- has been reported. This feature is one of the youngest and best preserved complex craters on Earth. Because of its remote Arctic setting, however, El gygytgyn crater remains poorly investigated. The objectives of this three-year project are to establish and maintain a research partnership between scientists from Russia and the United States interested in the El gygytgyn crater. The principal institutions in the U.S. will be the Geophysical Institute, University of Alaska Fairbanks and the University of Massachusetts Amherst. The principal institution in Russia will be the North East Interdisciplinary Scientific Research Institute (NEISRI), which is the Far-East Branch of the Russian Academy of Science. Three science tasks are identified for the exchange program: (1) Evaluate impactite samples collected during previous field excursions for evidence of and level of shock deformation. (2) Build a high-resolution digital elevation model for the crater and its surroundings using interferometric synthetic aperture radar techniques on JERS-1, ERS-1, ERS-2, and/or RadarSat range-doppler data. (3) Gather all existing surface data available from Russian and U.S. institutions (DEM, remote sensing image data, field-based lithological and sample maps, and existing geophysical data) and assemble into a Geographic Information Systems database.

Sharpton, Virgil L.↗

NASA NTRS1992

Imaging radar investigations of the Sudbury structure

This paper reports preliminary results of airborne imaging radar studies of the Sudbury structure carried out in preparation for a CCRS European Remote Sensing Satellite (ERS-1) investigation. The data used were synthetic aperture radar (SAR) C-band (5.66 cm) images acquired from about 6 km altitude in 1987. They cover the Sudbury area in both wide and narrow swath modes, with east-west flight paths and north-south illumination directions. Narrow swath resolution is 6 m in range and azimuth; wide swath resolution is 20 m in range and 10 m in azimuth. The STAR imagery has proven highly effective for field use, providing excellent rendition of topography and topographically expressed structure. Reasons for this include the illumination geometry, notably the look azimuth normal to the long axis of the Sudbury structure and Penokean fold axes, the good spatial resolution, and the short wavelength. Forested areas in the Sudbury area tend to be uniformly rough at C-band wavelength, with backscatter dominated by local incidence angle (i.e., topography). Field work using the SAR imagery has to date been concentrated in the North Range and Superior Province as far north as the Benny greenstone belt. This area was chosen for initial investigation of the original size and shape of the Sudbury structure because the effects of the Penokean Orogeny were minimal there. Field work using SAR indicates that there has been little postimpact deformation of the North Range or adjacent Superior Province rock. There appears to be no evidence for an outer ring concentric with the North Range as indicated by early Landsat imagery. The apparent ring shown by Landsat is visible on the SAR imagery as the intersection of two regional fracture patterns not related to the Sudbury structure. There is no outer ring visible southwest of the structure. This can reasonably be explained by Penokean deformation, but there is no outer ring to the northeast cutting the relatively undeformed Huronian sediments of the Cobalt Embayment.

Lowman, P. D.↗

DOE OSTI2022

Findings on Subtask 3.1 - Bakken Rich Gas Enhanced Oil Recovery Project

Total in-place oil for the Bakken petroleum system (BPS) (which includes the Bakken and Three Forks Formations) has been estimated to be 600 billion barrels (bbl). However, BPS wells have decline rates as high as 85% over the first 3 years of their lives, and primary recovery factors typically range from 3% to 10% of original oil in place. Given the low initial recovery rates, even small incremental productivity improvements could dramatically increase technically recoverable oil in the BPS. One potential solution is enhanced oil recovery (EOR) using gas injection, such as carbon dioxide (CO2) or hydrocarbon (HC) gases. While commonly used in conventional reservoirs, CO2 EOR in unconventional tight oil reservoirs has been limited to pilot tests. EOR using rich gas (mixture of methane, ethane, and propane) has also been employed in numerous pilots in several unconventional plays and has recently been successfully applied in the Eagle Ford play. If successful, large-scale gas-based EOR in the BPS could dramatically increase oil productivity and recovery factors and extend the life of the play for decades. While CO2 may be a technically suitable working fluid for EOR in the BPS, supplies are limited and costs for using CO2 in EOR pilots are prohibitively high. Meanwhile, produced gas flaring has presented challenges for BPS operators in North Dakota. Analysis conducted by the North Dakota Pipeline Authority indicates that the current gas-gathering infrastructure in North Dakota is insufficient to accommodate all of the associated gas that is produced from the BPS. The geographically isolated location of North Dakota relative to large natural gas markets, combined with suppressed natural gas prices, has made it economically challenging for industry to invest capital in expanding gas-gathering infrastructure in the state. These circumstances led to a research program conducted by the Energy & Environmental Research Center (EERC) in partnership with Liberty Resources Management Company LLC (LR) to examine the potential to use rich gas injection for EOR and mitigate flaring. A rich gas EOR pilot test was designed and executed by LR at its Stomping Horse development area in Williams County, North Dakota. From July 2018 through May 2019, a total of 160 million standard cubic feet (MMscf) of rich produced gas was injected into the BPS using five different wells in a sequential injection strategy. LR’s Leon–Gohrick drill spacing unit (DSU) was used as the test site. Regulatory oversight was provided by the North Dakota Industrial Commission (NDIC). Technical support was provided by the EERC through a series of laboratory, modeling, and field-based activities, and additional post-pilot research activities incorporated learnings from the test, developed new laboratory data, improved fracture modeling methods, and developed machine learning and big data analytics. The results from the Stomping Horse rich gas EOR pilot activities indicate that developing an effective, economical EOR approach for the BPS will require more field tests. Another key lesson learned from the Stomping Horse tests is that detailed pre- and posttest data on reservoir conditions and fluids production are essential. Robust reservoir characterization provides information that is crucial to creating realistic geomodels and conducting valid dynamic simulations of potential EOR scenarios. A detailed understanding of the completions and production history of offset wells is also necessary for valid test result interpretations. This knowledge is essential to designing the operational parameters of injectivity tests and interpreting the results. A conformance control strategy is also essential to success. Laboratory-based examinations of rich gas interactions with reservoir fluids and rocks were conducted, with an emphasis on determining the ability to mobilize oil in the tight reservoir rocks and shales of the BPS. Injection fluid composition was shown to have a positive impact on reducing reservoir oil minimum miscibility pressure (MMP), reducing interfacial tension (IFT), and altering wettability. IFT and contact angle measurements demonstrated that wettability can be altered in the presence of rich gas, suggesting the potential to improve oil recovery. Iterative modeling of surface infrastructure and reservoir performance using data generated by the various project activities was conducted. A geologic model of the Stomping Horse area was built; history-matched oil, gas, and water production was used in simulations of various EOR scenarios. Early programmatic modeling results were used to support LR’s design and operation of the EOR pilot and to provide insight regarding optimization of future commercial-scale BPS EOR design and operations. Post-pilot modeling focused on alternative methods of understanding complex fracture networks and accelerating simulation time. These led to improved simulation run times and provide excellent history-matching results. Several of these iterative models were used as the bases for developing algorithms into machine learning and big data analytics. History matching in reservoir simulation is time-consuming and computer processing-intensive. Machine learning algorithms were created, and an automated history-matching tool was developed. A large set of synthetic reservoir simulations were created to generate well responses (oil, gas, and water production, well bottomhole pressure [BHP], and tracer or propane breakthrough) for a set of EOR operating parameters that included offset well status (open or closed), injectate (rich gas or propane), injection rate, and injection well BHP. A user interface was developed to provide real-time visualization. Machine learning-based models were developed to provide rapid forecasting of well performance given a set of user-defined EOR operating parameters. These predictive models allow the user to modify the offset well status, injection rate, and injection well BHP and rapidly forecast future production performance. The combination of real-time visualization tools with real-time forecasting tools provides a framework for real-time control—operational changes that the EOR site operator can enact (e.g., changing gas injection rates) to affect the observed performance and potentially improve the EOR outcome. There is great reason to be optimistic about the future of EOR in the Bakken. The results of the laboratory studies suggest significant potential for high rates of oil mobilization using produced field gas injection under the right conditions. The results of the lab studies, combined with rigorous statistical analysis of well production data and associated modeling efforts, confirm the notion that fluid mobility within the reservoir is controlled by fractures. As more knowledge is gained about the nature and distribution of fracture networks in the Bakken, the industry will be in a better position to predict and, ultimately, influence fluid mobility. New field tests are necessary to develop a more complete understanding of those conditions. Thoughtful and creatively engineered field tests within a well-characterized geologic setting will yield the fundamental knowledge needed to take Bakken oil production to the next level. This subtask was cofunded through the EERC–U.S. Department of Energy Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FE0024233. Nonfederal funding was provided by the North Dakota Industrial Commission’s Oil and Gas Research Program and Computer Modelling Group.

04 OIL SHALES AND TAR SANDS↗

NASA NTRS1993

Comparison of inversion models using AIRSAR data for Death Valley, California

Polarimetric Airborne Synthetic Aperture Radar (AIRSAR) data were collected for the Geologic Remote Sensing Field Experiment (GRSFE) over Death Valley, California, USA, in September 1989. AIRSAR is a four-look, quid-polarizaiton, three frequency instrument. It collects measurements at C-band (5.66 cm), L-band (23.98 cm), and P-band (68.13 cm), and has a GIFOV of 10 meters and a swath width of 12 kilometers. Because the radar measures at three wavelengths, different scales of surface roughness are measured. Also, dielectric constants can be calculated from the data. The scene used in this study is in Death Valley, California and is located over Trail Canyon alluvial fan, the valley floor, and Artists Drive alluvial fan. The fans are very different in mineralogic makeup, size, and surface roughness. Trail Canyon fan is located on the west side of the valley at the base of the Panamint Range and is a large fan with older areas of desert pavement and younger active channels. The source for the material on southern part of the fan is mostly quartzites and there is an area of carbonate source on the northern part of the fan. Artists Drive fan is located at the base of the Black Mountains on the east side of the valley and is a smaller, young fan with its source mostly from volcanic rocks. The valley floor contains playa and salt deposits that range from smooth to Devil's Golf course type salt pinnacles.

Kierein-Young, Kathryn S.↗

NASA NTRS2006

Calibration of the EU Oxybarometer for Nakhlites

Martian meteorites have various characteristics, which are direct clues to understanding the petrogenesis of Mars rocks. The variation in oxidation state among the Martian meteorites must have important implications for redox conditions of the Martian crust/mantle and overall differentiation on Mars. Wadhwa [1] and Herd et al. [2] reported that Martian basalts were formed under a range of oxidation states, suggesting complex petrogenesis processes. The nakhlites, which have rather different characteristics from basaltic shergottites, may give us additional clues to Martian petrogenesis. The oxidation states of meteorites are usually described by the oxygen fugacity (fO2) under which the meteorites crystallized. One of the methods to estimate the oxygen fugacity is the depth of Eu anomaly. Eu(2+)/Eu(3+) is determined by the oxygen fugacity and partitioning is different for Eu(2+) and Eu(3+). Therefore, the depth of Eu anomaly in a mineral is a function of the oxygen fugacity and the Eu2+/Eu3+ in the melt from which the mineral crystallized. This method has some advantages over another major method, the two-oxide oxybarometer [3], which can more easily be affected by subsolidus processes. The Eu oxybarometer can analyze the cores of the earliest formed crystals in Martian meteorites, which means it can give us a better indication of the oxygen fugacity of the parent melt. The calibration of the Eu oxybarometer has been done with the basaltic shergottites before [4]. However, it has never been applied to nakhlites (Oe et al. [5] measured the depth of Eu anomaly in the synthetic pyroxene only at QFM). Partition coefficients are strongly affected by phase compositions, especially pyroxene Ca content and melt Al content [e.g., 5,6]. The composition of nakhlite pyroxene is rather different from basaltic shergottite pyroxene. Thus, there may be problems in applying the Eu oxybarometer calibration for the basaltic shergottites [7] to nakhlites. Thus, we report in this abstract preliminary results of our experimental calibration of the depth of Eu anomaly in pyroxene vs. oxygen fugacity for nakhlites.

Makishima, J.↗

NASA NTRS1992

Lithological and textural controls on radar and diurnal thermal signatures of weathered volcanic deposits, Lunar Crater region, Nevada

Radar backscatter intensity as measured by calibrated synthetic aperture radar (SAR) systems is primarily controlled by three factors: local incidence angle, wavelength-scale roughness, and dielectric permittivity of surface materials. Radar observations may be of limited use for geological investigations of surface composition, unless the relationships between lithology and the above characteristics can be adequately understood. In arid terrains, such as the Southwest U.S., weathering signatures (e.g. soil development, fracturing, debris grain size and shape, and hill slope characteristics) are controlled to some extent by lithologic characteristics of the parent bedrock. These textural features of outcrops and their associated debris will affect radar backscatter to varying degrees, and the multiple-wavelength capability of the JPL Airborne SAR (AIRSAR) system allows sampling of textures at three distinct scales. Diurnal temperature excursions of geologic surfaces are controlled primarily by the thermal inertia of surface materials, which is a measure of the resistance of a material to a change in temperature. Other influences include albedo, surface slopes affecting insolation, local meteorological conditions and surface emissivity at the relevant thermal wavelengths. To first order, thermal inertia variations on arid terrain surfaces result from grain size distribution and porosity differences, at scales ranging from micrometers to tens of meters. Diurnal thermal emission observations, such as those made by the JPL Thermal Infrared Multispectral Scanner (TIMS) airborne instrument, are thus influenced by geometric surface characteristics at scales comparable to those controlling radar backscatter. A preliminary report on a project involving a combination of field, laboratory and remote sensing observations of weathered felsic-to basaltic volcanic rock units exposed in the southern part of the Lunar Crater Volcanic Field, in the Pancake Range of central Nevada is presented. Focus is on the relationship of radar backscatter cross sections at multiple wavelengths, apparent diurnal temperature excursions identified in multi-temporal TIMS images, surface geometries related to weathering style, and parent bedrock lithology.

Plaut, Jeffrey J.↗

NASA NTRS1999

Carboxylic and dicarboxylic acids extracted from crushed magnesium oxide single crystals

Carboxylic and dicarboxylic acids (glycolic, oxalic, malonic and succinic) have been extracted with tetrahydrofuran (THF) and H2O from large synthetic MgO crystals, crushed to a medium fine powder. The extracts were characterized by infrared spectroscopy and 1H-NMR. The THF extracts were derivatized with tert-butyldimethylsilyl (t-BDMS) for GC-MS analysis. A single crystal separated from the extract was used for an x-ray structure analysis, giving the monoclinic unit cell, space group P21/c with ao = 5.543 A, bo = 8.845 A, co = 5.086 A, and beta = 91.9 degrees, consistent with beta-succinic acid, HOOC(CH2)COOH. The amount of extracted acids is estimated to be of the order of 0.1 to 0.5 mg g-1 MgO. The MgO crystals from which these organic acids were extracted grew from the 2860 degrees C hot melt, saturated with CO/CO2 and H2O, thereby incorporating small amounts of the gaseous components to form a solid solution (ss) with MgO. Upon cooling, the ss becomes supersaturated, causing solute carbon and other solute species to segregate not only to the surface but also internally, to dislocations and subgrain boundaries. The organic acids extracted from the MgO crystals after crushing appear to derive from these segregated solutes that formed C-C, C-H and C-O bonds along dislocations and other defects in the MgO structure, leading to entities that can generically be described as (HxCyOz)n-. The processes underlying the formation of these precursors are fundamental in nature and expected to be operational in any minerals, preferentially those with dense structures, that crystallized in H2O-CO2-laden environments. This opens the possibility that common magmatic and metamorphic rocks when weathering at the surface of a tectonically active planet like Earth may be an important source of abiogenically formed complex organic compounds.

NASA Discipline Exobiology↗

DOE OSTI2025

NdPO 4 solubility and aqueous Neodymium speciation in supercritical fluids: An experimental study at 500–700 °C and 1.7 kbar

A key aspect in the formation of rare earth elements (REE) deposits is the role of REE transport as aqueous REE complexes in supercritical hydrothermal solutions, where the nature of the aqueous complex is controlled by solution composition, temperature and pressure. Despite chloride being considered as one of the most abundant transporting ligands in magmatic-hydrothermal fluids, experimental investigations on the stability of aqueous REE chloride complexes are scarce above 300 °C. In this study, synthetic NdPO 4 crystals were reacted with non-saline and saline (0, 0.05 and 0.5 mNaCl), acidic (0.01 mHCl) aqueous solutions in a series of solubility experiments conducted at 500–700 °C and 1.7 kbar, where the solubilities were determined using a stable Nd isotope ( 145 Nd isotope spike) dilution technique. NdPO 4 solubility ranges between 28 ppm and 10,858 ppm, where solubility increases with both temperature and salinity. At 500 °C, log mNdPO 4 increases from –3.93 to –1.60 and there is a strong correlation between NdPO 4 solubility and NaCl concentrations (slope of 1.2 ± 0.3), indicating stabilization of the Nd chloride aqueous complexes with a stoichiometry corresponding to NdCl 2+ . At 600 °C, this correlation is weaker (slope of 0.4, log mNdPO 4 increases from –2.63 to –1.88) indicating the stabilization of both Nd chloride and hydroxyl species controlling solubility. At 700 °C, NdPO 4 solubility is largely independent of NaCl concentration indicating that solubility is controlled by Nd hydroxyl complexes, where stoichiometry suggests the neutral Nd(OH) 3 0 species is dominant. The solubility product (Ksp) of NdPO4 is derived from experimental data with the relation: log K sp = -41.81 – 0.057T – 20987/T, with T temperature in Kelvin. Comparison of the measured Nd phosphate solubility to thermodynamic predictions using the available Helgeson-Kirkham-Flowers equation of state parameters for aqueous Nd complexes indicate that predictions are up to three orders of magnitude lower compared to experimental observations. This discrepancy is most pronounced in saline solutions, suggesting that thermodynamic properties of the REE chloride species in supercritical fluids require revision. Numerical simulations of fluid-rock interaction between acidic, saline fluids and a Strange Lake felsic mineral assemblage demonstrates that NdPO 4 solubility predictions from models are four to six orders of magnitude lower than those calculated based on empirical fits from experiments, which suggests that acidic, saline fluids may play an important role in mobilizing large amounts of light REE from 450 to 700 °C.

58 GEOSCIENCES↗

NASA NTRS1998

Carboxylic and Dicarboxylic Acids Extracted from Crushed Magnesium Oxide Single Crystals

Carboxylic and dicarboxylic acids (glycolic, oxalic, malonic and succinic) have been extracted with tetrahydrofuran (THE) and H2O from large synthetic MgO crystals, crushed to a medium fine powder. The extracts were characterized by infrared spectroscopy and (sup 1)H-NMR (Nuclear Magnetic Resonance). The THF extracts were derivatized with tert-butyldimethylsilyl (t-BDMS) for GC-MS (Gas Chromatography - Mass Spectroscopy) analysis. A single crystal separated from the extract was used for an x-ray structure analysis, giving the monoclinic unit cell, space group P2(sub 1)/c with a(sub o) = 5.543 A, b(sub o) = 8.845 A, c(sub o) = 5.086 A, and beta = 91.9 degrees, consistent with beta-succinic acid, HOOC(CH2)COOH. The amount of extracted acids is estimated to be of the order of 0.1 to 0.5 mg/g MgO. The MgO crystals from which these organic acids were extracted grew from the 2360 C hot melt, saturated with CO/CO2 and H2O, thereby incorporating small amounts of the gaseous components to form a solid solution (ss) with MgO. Upon cooling, the ss becomes supersaturated, causing solute carbon and other solute species to segregate not only to the surface but also internally, to dislocations and subgrain boundaries. The organic acids extracted from the MgO crystals after crushing appear to derive from these segregated solutes that formed C-C, C-H, and C-O bonds along dislocations and other defects in the MgO structure, leading to entities that can generically be described as (HxCyOz)(sup n-). The processes underlying the formation of these precursors are fundamental in nature and expected to be operational in any minerals, preferentially those with dense structures, that crystallized in H2O-CO2-laden environments. This opens the possibility that common magmatic and metamorphic rocks when weathering at the surface of a tectonically active planet like Earth may be an important source of abiogenically formed complex organic compounds.

Freund, Friedemann↗

DOE OSTI2024

Bobfinchite, Na[(UO2)8O3(OH)11]·10H2O, a new Na-bearing member of the schoepite family

Abstract The new mineral bobfinchite (IMA2020-082), Na[(UO2)8O3(OH)11]·10H2O, was found in the Burro mine, Slick Rock district, San Miguel County, Colorado, U.S.A., where it occurs as an oxidation product of uraninite on asphaltite matrix in intimate association with gypsum, natrozippeite, metaschoepite, and uranopilite. Bobfinchite crystals are transparent to translucent, yellow, lozenge-shaped disks up to 0.3 mm wide. Crystals are flattened on [100] and exhibit the forms {100}, {011}, {021}, {021}, and {011}. Bobfinchite has a pale-yellow streak and emits very dim yellow fluorescence under 365 nm ultraviolet illumination. The crystals are brittle with very good {100} cleavage and irregular, stepped fracture. The Mohs hardness is ca. 2 based on scratch tests. The calculated density is 5.044 g/cm3 based on the empirical formula and 5.036 g/cm3 for the ideal formula. Bobfinchite is optically biaxial (–), with α = 1.690(5), β = 1.7205(5), and γ = 1.730(5) (white light). The measured 2V, estimated from the interference figure, is 55(5)° and the calculated value is 59.1°. Dispersion is moderate, r > v; orientation: X = a, Y = b, Z = c; pleochroism: X nearly colorless, Y yellow, Z yellow; X < Y ≈Z. Electron microprobe analysis provided the empirical formula (Na0.99Pb0.02)[(UO2)7.99O3(OH)11]·10H2O. The five strongest X-ray powder diffraction lines are [dobs in Å(I)(hkl)]: 7.34(100)(200), 3.59(50)(024), 3.23(60)(224), 3.18(36)(240), and 2.01(23)(624,551,208,640,346). Bobfinchite is orthorhombic, Pbcn, a = 14.6249(9), b = 14.0389(10), c = 16.6923(10) Å, V = 3427.2(4) Å3, and Z = 4. The structure of bobfinchite (R1 = 0.0330 for 3770 I > 4σI) is built from uranyl oxide-hydroxide sheets that adopt the fourmarierite topology, with interlayer Na+ and H2O groups. Both the sheet and interlayer topology mimic those observed in natural and synthetic Na-metaschoepites studied previously, and as seen in other uranyl oxide hydrate minerals, charge balance is achieved at specific sites in the sheet through the substitution O2– ↔ (OH)–.

Geochemistry & Geophysics↗

NASA NTRSDate not supplied

Olivine Dissolution and Formation of Secondary phases in Ultramafic Soils

Introduction: Olivine has been proposed as an indicator for the duration of water-rock interaction within Martian rocks and sediments [1-3]. The use of olivine as a mineralogical indicator for past aqueous alteration on Mars requires interpretation of a complex combination of factors including pH, temperature, and composition [5,6]. Here, we examine the persistence of natural olivine within terrestrial ultramafic soils (Fe/Mg-rich, Al-poor) developing under different climatic conditions and the incipient dissolution of emplaced forsterite (Fo) and fayalite (Fa) surfaces to investigate environmental effects on incipient olivine dissolution, olivine persistence in soils, and formation of secondary phases. Methods: Field Sites. We examined olivine weathering and secondary material formation in ultramafic soils at 6 sites in the Klamath Mountains (KM) of northern California with a mean annual temperature of ~12.8℃ and precipitation of ~55.7-95.4 cm/year [7], and soil pH of ~6.5-7.3; 4 sites in the Tablelands (TB) of Newfoundland, Canada with a mean annual temperature of <3.9℃ and precipitation of ~120.0 cm/year [8], and soil pH of ~7.7; and at 3 sites at Pickhandle Gulch (PG), Nevada with a mean annual temperature of ~14.4℃ and precipitation of ~14.1 cm/year [7], and soil pH of ~8.5. Sampling sites span an age range of ~12.1-50+ kya in the Klamath Mountains [9,10] and ~13-30 kya in the Tablelands [11]. Pickhandle Gulch sites are undated. Parent Material and Soil Analyses. Polished thin sections of bulk soil prepared by Wagner Petrographic, Inc were carbon-coated and analyzed on a JEOL 2100 SEM in back-scattered electron mode in the EMIL lab at UNLV and at the 13-ID-E synchrotron beamline at Argonne National Laboratory using µXRF, µXRD, and XAS. Soil and parent material samples were powdered in a Fritsch pulverisette and analyzed by XRD and soil by VNIR. Soil preparation is further described in [12]. Disk Preparation, Burial, and Collection. Fo disks were cut from a column prepared via hot-pressing and Fa disks by sintering synthetic fayalite powder, see [13] for detail. Disks were polished to a 0.25-micron level with diamond grit. Disks were buried in 3 KM soils, 4 TB soils, and 3 PG soils, collected after exactly 365 days, and washed gently with 100% reagent grade ethanol to remove potential adhered soil material. Weathered disks and soil samples were stored in a -20℃ freezer until analysis. Unaltered control disks prepared identically to the buried disks were stored at -20℃ for the duration of the experiment. Disk Analyses. One Fo and Fa disk from each climate zone was analyzed on a variable pressure Zeiss Supra 40VP SEM at Northern Arizona University. A separate Fo and Fa disk from each climate zone was analyzed by XPS using a Physical Electronics VersaProbe II at the Penn State Univ. Materials Characterization Lab after a Na-dodecyl sulfate wash and ozonation to remove carbon contamination as in [14]. VNIR measurements were conducted at Johnson Space Center using an ASD FieldSpec3 under ambient lab conditions on a separate Fo and Fa disk from each climate zone. One separate Fo and Fa control sample was analyzed for each technique for comparison with weathered samples. XPS uncertainty was determined from 5 repeat measurements on controls. Results: Bedrock and Soil Results Olivine is present in the parent material in the KM and TB. Olivine is found in ~12.1 ka KM soils but is absent from all older soils, while persisting into the oldest (>20 ka) TB soil (Figure 1). In both locations, olivine is found as cores surrounded by a serpentine rind (Figure 2). VNIR spectra from the analyzed soils possess strong OH-associated spectral features at ~2.33 µm indicating the presence of Mg-rich phyllosilicates as well as ferric-oxide features at ~0.92 µm in the KM (Figure 3). Primary crystalline silicate grains mostly incorporate Fe2+, while poorly crystalline weathering rinds are best fit by ferric oxide XAS standards (Figure 4). µXRF also shows that Fe and Ni concentrate in weathering rinds and Cr remains within interior silicate grains (Figure 4). Buried Sample Results All Fo surfaces exhibited formation of dissolution features including shallow pitting not observed on controls. Dissolution features were most visually widespread on the KM disk (Figure 5). Leaching of Mg from KM and TB Fo disks was evident from <1.6 Mg/Si ratios measured by XPS (Figure 6). Fe-rich precipitates in SEM (Figure 5) and Fe presence in XPS scans (Figure 6) indicate Fe deposition onto KM and TB Fo disk surfaces. The appearance of a spectral feature at 0.55 µm in the VNIR spectra from the TB Fo suggests this Fe is ferric (Figure 7). The PG Fo appears least altered, with minimal formation of dissolution features in SEM (Figure 5), a Mg/Si ratio inconsistent with leaching (~2) (Figure 6), and VNIR spectra almost identical to the control sample. Analysis of Fa surfaces is ongoing. The higher temperatures and more acidic pH in the KM soils likely drive the faster dissolution of the Fo disks described above. While the TB soils experience greater precipitation than in the KM, the cooler temperatures and more basic soil pH facilitate observable but more limited alteration. The dry climate and basic soil pH at PG lead to minimal dissolution of the PG disk surfaces.

A D Feldman↗