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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Rapid AI-based Dissection of Ashes using Raman and XRF Spectroscopy (RADAR-X)

Waste-to-energy (WTE) facilities incinerate ~35 million tons of municipal solid waste annually in the United States. The incineration process reduces the mass and the volume of the waste fraction by over 75 and 95%, respectively. The fraction left after incineration remains as ash residues and is referred to as WTE ash, compromising of bottom and fly ash. In the United States, ~10 million tons of WTE ashes are generated annually and predominantly landfilled because of the lack of secondary end-use pathways. This incurs a significant financial burden (landfilling costs) on U.S. WTE facilities and also results in the loss of materials to the landfill. The primary objective of this research is to understand better the elemental and mineralogical composition of WTE ashes from diverse origins and find composition dependent upcycling pathways for diverting these ashes from landfills. This primary objective was addressed through three research tasks –(Task I) An AI-led Multi-Modal Approach for Compositional Analysis, (Task II) Developing a Dissolution-Based Test for Real Time Analysis, and (Task III) Establishing composition-dependent end uses. The chemical composition of WTE ash is dependent on two factors, i.e., the input waste composition and the operational parameters of a WTE facility (combustion conditions). Amongst these two factors, the input waste composition will likely show spatial and temporal variation. As a result, the chemical composition of WTE ash will also fluctuate. To understand the spatial and temporal variation in WTE ash composition, in Task I, we collected 128 ash samples (62 bottom ash and 66 fly ash samples) from 11 WTE facilities located in 11 U.S. states and characterized them via X-ray Fluorescence, powder X-ray Diffraction, and Raman Spectroscopy. The findings from this extensive characterization work indicated that the key elements in WTE fly ashes are Ca, Cl (greater than 10 wt. %), Si, S, K, Zn ( between 1 and 10 wt. %), Mg, Al, P, Ti, Fe, Cu, Br, and Pb (between 0.1 and 1 wt. %). Similarly, the key elements in WTE bottom ash fraction finer than 45μm are Ca (greater than 10 wt. %), Mg, Al, Si, S, Cl, K, Ti, Fe, Zn (between 1 and 10 wt. %), P, V, Cr, Mn, Cu, Br, and Pb (between 0.1 and 1 wt. %). Here, we note that the dominant fraction of WTE bottom ash is the coarse fraction. The coarse WTE bottom ash fraction (rich in silicon) was not characterized in this study because of excessive grinding requirements and their unsuitability as a supplementary cementitious material due to their coarse nature. The elements in WTE bottom ashes are present as calcite, anhydrite, vaterite, hydroxyapatite, quartz, bassanite, gehlenite, akermanite, hydrocalumite, and portlandite. Similarly, the mineralogical species present in WTE fly ashes are calcium chloride hydroxide, halite, calcite, anhydrite, sylvite, hydrocalumite, vaterite, hannebachite, quartz, and bassanite. Temporal variation in ash composition may also result in significant fluctuations in chemical compositions. Therefore, a WTE facility may need to monitor the ash composition (elemental and mineralogical composition) in real time. In Task I, we evaluated the possibility of using a portable X-ray fluorescence (XRF) spectrometer to monitor the elemental composition in real-time. Specifically, we collected XRF data on identical specimens via a portable XRF spectrometer (low-end) and a lab-based benchtop XRF spectrometer (high-end). The collected data was used to train an A.I. algorithm (portable XRF data as an input and benchtop XRF data as an output) to predict accurate elemental composition using portable XRF data. Finally, we developed a 2-minute photobleaching protocol to monitor the mineralogical characteristics of WTE ashes via Raman spectroscopy. Overall, the activities in Task I improved our understanding of ash composition and developed techniques to monitor elemental and mineralogical composition in near real-time. Based on the findings of Task I, we find that WTE ashes exhibit wide variability in mineralogy. For ICP-based elemental analysis, all the mineralogical species in WTE ashes must be brought into solution. This is traditionally accomplished with acid digestion using a combination of multiple acids. However, acid digestion with multiple acids is time-consuming and often fails to ensure complete digestion of the ash matrix. To address this limitation, in Task II, we developed an alkali-fusion-based digestion protocol using a combination of lithium tetraborate, lithium metaborate, and their combinations as possible alkali fluxes for digesting WTE ashes entirely and rapidly. The validity of the developed method was evaluated on two standard ash specimens, i.e., SRM 1633c coal fly ash and BCR-176R incineration fly ash specimen. The findings suggest that the developed protocol can ensure complete digestion of elements such as Al, Ba, Ca, Cr, Cu, Mg, Mn, P, Sr, V, Zn, Be, K, and rare earth elements. The recent changes in the energy market towards renewables and increased metal recycling have resulted in reduced supplies of supplementary cementitious materials (coal fly ash and slag). Therefore, in Task III, we evaluated the possibility of employing WTE ashes as SCMs. As the chemical composition of WTE ashes varies temporally (on an hourly basis), there was also a need to develop tests that can evaluate the suitability of material to act as supplementary cementitious material rapidly, i.e., in a few minutes. Therefore, in Task II, we also developed a rapid test to assess the suitability of a material to act as an SCM in 5 minutes. This represents a significant advance over the state-of-the-art R 3 test, which takes ~144 hours. This test was initially validated on amorphous aluminosilicates, such as calcined clays, and could be extended to evaluate other industrial by-products, such as WTE ashes. In Task III, we evaluated the possibility of employing WTE ashes for two applications, i.e., as an SCM and a lime substitute for clay stabilization. The findings from Task I indicated that WTE ashes are enriched in chlorine and, therefore, cannot be used directly as an SCM due to corrosion-related risks and altered hydration kinetics. Accordingly, we developed an ash treatment protocol to reduce the solubility of chlorine-containing species in WTE ashes. The developed treatment protocol also immobilized lead in certain mineral forms. As a result of the treatment, WTE ashes can be used as SCMs without any corrosion or heavy metal leaching concerns. The second application examined in this study was clay stabilization. WTE ashes are calcium-rich and can be an adequate lime replacement for clay stabilization. Our findings reveal that the sum of the concentrations of Ca(OH) 2 and CaClOH controls the clay stabilization capability of WTE ashes. In summary, in this work, we evaluated the elemental and mineralogical characteristics of U.S. WTE ashes from diverse origins and developed tests to evaluate the chemical characteristics of these ashes in real time through a portable XRF and a benchtop Raman spectrometer. Based on the chemical characteristics of these ashes, we developed an ash treatment process to enable the use of WTE ashes as an SCM and also evaluated the possibility of employing these ashes for clay stabilization. Overall, the findings from this work enables the diversion of WTE ashes from landfills for multiple end-uses, i.e., as an SCM or a lime substitute for clay stabilization.

36 MATERIALS SCIENCE↗
NASA NTRS1998

The Athena Mars Rover Science Payload

The Mars Surveyor missions that will be launched in April of 2001 will include a highly capable rover that is a successor to the Mars Pathfinder mission's Sojourner rover. The design goals for this rover are a total traverse distance of at least 10 km and a total lifetime of at least one Earth year. The rover's job will be to explore a site in Mars' ancient terrain, searching for materials likely to preserve a record of ancient martian water, climate, and possibly biology. The rover will collect rock and soil samples, and will store them for return to Earth by a subsequent Mars Surveyor mission in 2005. The Athena Mars rover science payload is the suite of scientific instruments and sample collection tools that will be used to perform this job. The specific science objectives that NASA has identified for the '01 rover payload are to: (1) Provide color stereo imaging of martian surface environments, and remotely-sensed point discrimination of mineralogical composition. (2) Determine the elemental and mineralogical composition of martian surface materials. (3) Determine the fine-scale textural properties of these materials. (4) Collect and store samples. The Athena payload has been designed to meet these objectives. The focus of the design is on field operations: making sure the rover can locate, characterize, and collect scientifically important samples in a dusty, dirty, real-world environment. The topography, morphology, and mineralogy of the scene around the rover will be revealed by Pancam/Mini-TES, an integrated imager and IR spectrometer. Pancam views the surface around the rover in stereo and color. It uses two high-resolution cameras that are identical in most respects to the rover's navigation cameras. The detectors are low-power, low-mass active pixel sensors with on-chip 12-bit analog-to-digital conversion. Filters provide 8-12 color spectral bandpasses over the spectral region from 0.4 to 1.1 micron Narrow-angle optics provide an angular resolution of 0.28 mrad/pixel, nearly a factor of four higher than that of the Mars Pathfinder and Mars Surveyor '98 cameras. Image compression will be performed using a wavelet compression algorithm. The Mini-Thermal Emission Spectrometer (Mini-TES) is a point spectrometer operating in -the thermal IR. It produces high spectral resolution (5 /cm) image cubes with a wavelength range of 5-40 gm, a nominal signal/noise ratio of 500:1, and a maximum angular resolution of 7 mrad (7 cm at a distance of 10 in). The wavelength region over which it operates samples the diagnostic fundamental absorption features of rockforming minerals, and also provides some capability to see through dust coatings that could tend to obscure spectral features. The mineralogical information that Mini-TES provides will be used to select from a distance the rocks and soils that will be investigated in more detail and ultimately sampled. Mini-TES is derived from the MO/MGS TES instrument, but is significantly smaller and simpler. The instrument uses an 8-cm Cassegrain telescope, a Michelson interferometer, and uncooled pyroelectric detectors. Along with its mineralogical capabilities, Mini-TES can provide information on the thermophysical properties of rocks and soils. Viewing upward, it can also provide temperature profiles through the martian atmospheric boundary layer. Elemental and Mineralogical Composition: Once promising samples have been identified from a distance using Pancam/Mini-TES, they will be studied in detail using up to three compositional sensors that can be placed directly against them by an Instrument Arm. The two compositional sensors, presently on the payload are an Alpha-Proton-X-Ray Spectrometer (APXS), and a Mossbauer Spectrometer. The APXS is derived closely from the instrument that flew on Mars Pathfinder. Radioactive alpha sources and three detection modes (alpha, proton, and x-ray) provide elemental abundances of rocks and soils to complement and constrain mineralogical data. The Athena APXS will have a revised mechanical design that will cut down significantly on backscattering of alpha particles from martian atmospheric carbon. It will also include a target of known elemental composition that will be used for calibration purposes. The Athena Mossbauer Spectrometer is a diagnostic instrument for the mineralogy and oxidation state of Fe-bearing phases, which are particularly important on Mars. The instrument measures the resonant absorption of gamma rays produced by a Co-57 source to determine splitting of nuclear energy levels in Fe atoms that is related to the electronic environment surrounding them. It has been under development for space flight for many years at the Technical University of Darmstadt. The Mossbauer Spectrometer (and the other arm instruments) will be able to view a small permanent magnet array that will attract magnetic particles in the martian soil. The payload may also include a Raman Spectrometer. If included, the Raman Spectrometer will provide precise identification of major and minor mineral phases. It requires no sample preparation, and is also sensitive to organics. Fine-Scale Texture: The Instrument Arm a also carries a Microscopic Imager that will obtain high-resolution monochromatic images of the same materials for which compositional data will be obtained. Its spatial resolution is 20 micron/pixel over a 1 cm depth of field, and 40 micron/pixel over a 1-cm depth of field. Like Pancam, it uses the same active pixel sensor detectors and electronics as the rover's navigation cameras. The Instrument Arm is a three degree-of-freedom arm that uses designs and components from the Mars Pathfinder and Mars Surveyor '98 projects. Its primary function is instrument positioning. Along with the instruments noted above, it also carries a brush that can be used to remove dust and other loose coatings from rocks. Sample Collection and Storage: Martian rock and soil samples will be collected using a low-power rotary coring drill called the Mini-Corer. An important characteristic of this device is that it can obtain intact samples of rock from up to 5 cm within strong boulders and bedrock, Nominal core dimensions are 8xl7 mm. The Mini-Corer drills a core to the commanded depth in a rock, shears it off, retains it, and extracts it. It can also acquire samples of loose soil, using soil sample cups that are pressed downward into loose material. The Mini-Corer can drill at angles from vertical to 45' off vertical. It has six interchangeable bits for long life. Mechanical damage to the sample during drilling is minimal, and heating is negligible. After acquisition, the sample may be viewed by the arm instruments, and/or placed in one of 104 compartments in the Sample Container. A subset of the acquired samples may be replaced with other samples obtained later if desired. The Sample Container has no moving parts, and is mounted external to the rover for easy removal by the Mars Surveyor 2005 flight system. Operation of the rover will make extensive use of automated onboard navigation and hazard avoidance capabilities. Otherwise, use of onboard autonomy is minimal. Data downlink capability is about 40 Mbit/sol, and the use of the Mars Surveyor '01 orbiter for data relay imposes a limit of at most two command cycles per sol. Because of the significant amount of time available between command cycles, all payload elements will be operated sequentially, rather than in parallel.; this approach also significantly simplifies operations and minimizes peak power usage. The landing site for the '01 rover has not been selected yet. Site selection will make as full use as possible of Mars Global Surveyor data, and will involve substantial input from the broad Mars science community. Summary: The following table describes the mass, power, providers, and key scientific objectives of all the major elements of the Athena payload. Additional Athena payload information may be found at: http://astrosun.tn.cornell.edu/athena/index.html. Additional information contained in the original.

Squyes, S. W.↗
NASA NTRS2016

Precision Oxygen Isotope Measurements of Two C-Rich Hydrated Interplanetary Dust Particles

Introduction: Chondritic-smooth IDPs (Interplanetary Dust Particles) are low porosity objects whose mineralogy is dominated by aqueous alteration products such as Mg-rich phyllosilicates (smectite and serpentine group) and Mg-Fe carbonate minerals. Their hydrated mineralogy combined with low atmospheric entry velocities have been used to infer an origin largely from asteroidal sources. Spectroscopic studies show that the types and abundance of organic matter in CS IDPs is similar to that in CP IDPs. Although CS IDPs show broad similarities to primitive carbonaceous chondrites, only a few particles have been directly linked to specific meteorite groups such as CM and CI chondrites based on the presence of diagnostic minerals. Many CS IDPs however, have carbon contents that greatly exceed that of known meteorite groups suggesting that they either may derive from comets or represent samples of more primitive parent bodies than do meteorites. It is now recognized that many large, dark primitive asteroids in the outer main belt, as well as some trans-Neptunian objects, show spectroscopic evidence for aqueous alteration products on their surfaces. Some CS IDPs exhibit large bulk D enrichments similar to those observed in the cometary CP IDPs. While hydrated minerals in comets have not been unambiguously identified to date, the presence of the smectite group mineral nontronite has been inferred from infrared spectra obtained from the ejecta from comet 9P/Tempel 1 during the Deep Impact mission. Recent observations of low temperature sulfide minerals in Stardust mission samples suggest that limited aqueous activity occurred on comet Wild-2. All of these observations, taken together, suggest that the high-carbon hydrated IDPs are abundant and important samples of primitive solar system objects not represented in meteorite collections. Oxygen isotopic compositions of chondrites reflect mixing between a 16O-rich reservoir and a 17O,18O-rich reservoir produced via mass-independent fractionation. The composition of the 16O-rich reservoir is well constrained but material representing the 17O,18O-rich end-member is rare. Self-shielding models predict that cometary water, presumed to represent this reservoir, should be enriched in 17O and 18O by greater than 200 per mille. The high-carbon hydrated IDPs may be among the best materials available to search for preserved "cometary" H2O signatures. In order to better understand the origin and evolution of these particles, we have obtained 10 hydrated interplanetary dust particles for coordinated mineralogical, isotopic and organic analyses. We have previously reported the results of mineralogical and O isotopic measurements of two hydrated IDPs; here we present results of O isotopic measurements of three additional IDPs. Samples and Methods: Three interplanetary dust particles (L2079C35, L2083D46 and L2083E46) were embedded in S and partially ultramicrotomed into approximately 70 nanometer sections for analysis via transmission electron microscopy (TEM). The remainders of the unsliced particles were removed from S and pressed into high purity Au foil that was cleaned with HF acid and annealed at 800 degrees Centigrade. The pressed IDPs were analyzed via electron microprobe analysis (EPMA) for quantitative bulk chemical analysis. After EPMA analysis, the IDPs were subjected to precision O isotope analysis with the UCLA Cameca IMS-1270 ion probe. A 20 kiloelectronvolt, 0.5 nanoangstrom Cs+ primary beam of approximately 15 micrometers diameter was used for each measurement. Small particles of San Carlos olivine and Burma spinel were pressed into the Au foil for use as standards to correct for instrumental mass fractionation. The detection system was configured for multicollection, with 16O measured on a Faraday cup, and 17O and 18O measured on electron multipliers (EMs). Individual analyses consisted of 15 cycles of 10 seconds per cycle. Additionally, two microtome thin sections were measured for H isotopic compositions with the JSC NanoSIMS 50L ion probe. An 8 picoangstrom, 16 kiloelectronvolt Cs plus primary beam was used. Measurements consisted of H, C, 12C, 16O, and 18O collected with EMs in multicollection. Terrestrial biotite and kerogen were used for isotopic standards. A significant challenge in O isotope measurement of hydrated minerals is the interference from 16OH at mass 17O. We ensured that the 17O and 16OH peaks were fully resolved by using a mass resolution of greater than 7000 and by careful analyses of San Carlos olivine, Burma spinel and chlorite hydrated mineral standards. The hydride was further suppressed with a cold finger attached to an LN2 dewar to trap volatiles in the sample chamber. All sputtered ions were counted (i.e. presputtering was not used); after applying background, yield and deadtime corrections, we performed a change-point analysis on our data via R in order to determine when the sample reached sputtering equilibrium; data points collected prior to the change point were excluded. Change-point analysis was also used to determine whether the IDP had completely sputtered. Results: Mineralogy. IDPs C35 and E46 exhibited hydrated mineralogies, Fe-Ni sulfide grains, nanoglobules and occasional enstatite grains distributed throughout a fine-grained Mg-Fe saponite matrix. C35 also contained breunnerite (Mg,Fe)CO3; solar flare tracks were observed in enstatite, indicating minimal atmospheric entry heating. The mineralogy of D46 is dominated by a large FeS grain with a minor component of adhering silicate material. D46 was strongly heated during atmorpheric entry as evidenced by a well-developed magnetite rim. EPMA analyses show that both C35 and E46 have high carbon contents of 20 weight percentage (approximately 6X CI). D46 contains approximately 6 wt.weight percentage C. A significant amount of the carbon is present as carbon nanoglobules. Results: Hydrogen isotopes: Although the bulk delta D values of both sections of L2079C35 were within error of SMOW (minus 33 plus or minus 19 per mille, 1 plus or minus 14 per mille 1 sigma), several delta D-rich hotspots were also identified, reaching 2000 per mille. As shown in Fig. 1, these hotspots are clearly associated with discrete carbonaceous inclusions that are akin to nanoglobules found in many meteorites and other IDPs. Oxygen Isotopes. Results of the oxygen isotope measurements are shown in Figure 1. The oxygen isotope composition for L2079C35 was delta 18O equals plus11.6 plus or minus 1.9per mille, delta 17O equals plus 7.9 plus or minus 1.9per mille (2 standard errors). The oxygen isotope composition for L2083D46 was delta 18O equals minus 8.1 plus or minus 1.9 per mille, delta 17O equals minus 6.4 plus or minus 3.1 per mille (2 standard errors). The oxygen isotope composition for L2083E46 was delta 18O equals plus 12.0 plus or minus 1.9 per mille, delta 17O equals plus 9.2 plus or minus 2.0 per mille (2 standard errors). Discussion: Despite mineralogical similarities to highly aqueously altered carbonaceous chondrites, the hydrated IDPs we analyzed have oxygen isotopic compositions that are distinct from matrix materials in the CI, CM, and CR chondrites. The IDPs plot along the Young-Russell line, with delta 17O values for C35 and E46 suggestive of interaction with a 16O-poor reservoir. However, we have thus far not observed evidence of extreme 16O-poor reservoirs expected from self-shielding models and observed in Acfer 094 simplectite. The high carbon contents of the IDPs also set them apart from known meteoritic samples. The lack of atmospheric entry heating effects are consistent with low encounter velocities and suggest either an asteroidal source, or a low inclination, low eccentricity cometary origin. Conclusions: The unusual oxygen isotopic compositions, high carbon contents, and the abundance of Drich nanoglobules, together, suggest that the high-carbon, hydrated IDPs are derived from a primitive source that is not yet represented in meteorite collections.

Snead, C. J.↗
NASA NTRS2024

Revision 1: Characterizing Basalt-Atmosphere Interactions on Venus: A Review of Thermodynamic and Experimental Results

The surface of Venus is in contact with a hot (~470° C), high pressure (92 bars), and caustic (CO 2 with S, but little H 2 O) atmosphere, which should cause progressive alteration of the crust in the form of sulfate and iron-oxide coatings; however, the exact rate of alteration and mineral species are not well constrained. Different experimental approaches, each with its own limitations, are currently being used to constrain mineralogy and alteration rate. One note is that no experimental approach has been able to fully replicate the necessary conditions and sustain them for a significant length of time. Further, geochemical modeling studies can also constrain surface alteration mineralogy, again with different assumptions and limitations. Here we review recent geochemical modeling and experimental studies to constrain the state of the art for alteration mineralogy, rate of alteration, open questions about the surface mineralogy of Venus, and what can be constrained before the fleet of missions arrive later this decade. Combining the new results confirm that basalt on the surface of Venus should react quickly and form coatings of sulfates and iron-oxides; however, the mineralogy and rate of alteration is dependent on physical properties of the protolith (including bulk composition, mineralogy, and crystallinity), as well as atmospheric composition, and surface temperature. Importantly, the geochemically modelling results show that the mineralogy is largely controlled by atmospheric oxygen fugacity, which is not well constrained for the near surface environment on Venus. Therefore, alteration experiments run over a range of oxygen and sulfur fugacities are needed across a wide range of Venus analog materials with varying mineralogy and crystallinity.

Justin Filiberto↗
NASA NTRS2006

Comet Dust After Deep Impact

When the Deep Impact Mission hit Jupiter Family comet 9P/Tempel 1, an ejecta crater was formed and an pocket of volatile gases and ices from 10-30 m below the surface was exposed (A Hearn et aI. 2005). This resulted in a gas geyser that persisted for a few hours (Sugita et al, 2005). The gas geyser pushed dust grains into the coma (Sugita et a1. 2005), as well as ice grains (Schulz et al. 2006). The smaller of the dust grains were submicron in radii (0-25.3 micron), and were primarily composed of highly refractory minerals including amorphous (non-graphitic) carbon, and silicate minerals including amorphous (disordered) olivine (Fe,Mg)2SiO4 and pyroxene (Fe,Mg)SiO3 and crystalline Mg-rich olivine. The smaller grains moved faster, as expected from the size-dependent velocity law produced by gas-drag on grains. The mineralogy evolved with time: progressively larger grains persisted in the near nuclear region, having been imparted with slower velocities, and the mineralogies of these larger grains appeared simpler and without crystals. The smaller 0.2-0.3 micron grains reached the coma in about 1.5 hours (1 arc sec = 740 km), were more diverse in mineralogy than the larger grains and contained crystals, and appeared to travel through the coma together. No smaller grains appeared at larger coma distances later (with slower velocities), implying that if grain fragmentation occurred, it happened within the gas acceleration zone. These results of the high spatial resolution spectroscopy (GEMINI+Michelle: Harker et 4. 2005, 2006; Subaru+COMICS: Sugita et al. 2005) revealed that the grains released from the interior were different from the nominally active areas of this comet by their: (a) crystalline content, (b) smaller size, (c) more diverse mineralogy. The temporal changes in the spectra, recorded by GEMIM+Michelle every 7 minutes, indicated that the dust mineralogy is inhomogeneous and, unexpectedly, the portion of the size distribution dominated by smaller grains has a more diverse mineralogy. The lower spatial resolution, high sensitivity Spitzer IRS data reveal resonances of refractory minerals (those seen by GEMINI+Michelle plus ortho-pyroxene)) as well resonances that can be attributed to phillosilicates (layer lattice silicates such as Montmorillonite) (Lisse et al. 2006). Pre- and post-impact, micron to submicron grains were deciphered to be present in the coma by the modeling the high spatial resolution images to account for nucleus plus inner coma fluxes (Wooden et al. 2005, 2006; Harker et al. 2005, 2006a). Note also that crystalline silicates were released from the interior of 73P-B/SW-3 as it disintegrated (Harker et al. 2006b). From the Deep Impact and the disintegration of 73P-B, we are led to ask the questians: Why is the mineralogy of the dust released from a volatile-rich pocket beneath the surface different from the dust that is released from the nominally active areas? Could the most volatile pockets be exhausted quickly? Why would crystalline silicates be associated with more volatile materials? Perhaps the structure of the comet is so inhomogeneous, e.g., the layered pile mode2 of the nucleus (Belton et al. 2006), that a reservoir of crystalline silicate and submicron grains just happens to not be released by the nominally active areas of comet 9P? Perhaps comets lose matter through their mantles from below their surfaces, thus preserving ancient topographic structures and radiation damaged silicates and carbon? We will discuss and ponder different scenarios. We will discuss future directions for coordinated observations of JF comets.

Wooden, Diane H.↗
DOE OSTI2021

Novel Geochemistry Determined from High Pressure, High Temperature Simulation Experiments of Hydraulic Fracture Test Site 2

A standard method in unconventional oil and gas production is the process of hydraulic fracturing followed by a shut-in period, during which the fracture fluid remains pressurized in the reservoir for up to three weeks before production begins. Despite this widely used process, very little is known about what occurs in the reservoir during this shut-in process. In order to properly delineate potential reservoir reactions that may occur during shut-in that would lead to corrosion and scaling events, experiments were conducted in high pressure, high temperature reactors to simulate conditions of the Wolfcamp Formation in the Delaware Basin. Experimental design allowed the assessment of the effect of proppant, microbiology, and time on the mineralogy and fluid chemistry in the reservoir. Results suggest the biggest impact on fluid chemistry and shale mineralogy during shut-in is time. Analyses demonstrate dissolution of the shale material, with maximum dissolved ions occurring after 7 days of the shut-in period. After 21 days, results suggest precipitation occurs. The Delaware Basin is demonstrated to be high in sulfate content, which further increases in the fluid due to dissolution reactions during shut-in. The pressure vessel experiments suggest there was no significant contribution to reactions from microbiology during the shut-in period. Furthermore, early production samples demonstrate a significant selection of the microorganism Caminicella, a genus of which has previously been correlated to corrosion and sulfide production. Results suggest shut-in conditions may provide high sulfate concentrations that could later be utilized by a shifted microbial community to drive potential well infrastructure failure. This is the first study to incorporate microbiology, mineralogy, and fluid chemistry to investigate the fundamental geochemical reactions that occur during shut-in and early phase production of the Delaware Downloaded from http://onepetro.org/URTECONF/proceedings-pdf/21URTC/2-21URTC/D021S032R001/2477425/urtec-2021-5219-ms.pdf/1 by Carol Worster on 28 February 2022 Basin. Results from this study can complement observations from the Hydraulic Fracture Test Site 2 observations

58 GEOSCIENCES↗
NASA NTRS2004

Reflectance and Thermal Infrared Spectroscopy of Mars: Relationship Between ISM and TES for Compositional Determinations

Reflectance spectroscopy has demonstrated that high albedo surfaces on Mars contain heavily altered materials with some component of hematite, poorly crystalline ferric oxides, and an undefined silicate matrix. The spectral properties of many low albedo regions indicate crystalline basalts containing both low and high calcium pyroxene, a mineralogy consistent with the basaltic SNC meteorites. The Thermal Emission Spectrometer (TES) experiment on the Mars Geochemical Surveyor has acquired critical new data relevant to surface composition and mineralogy, but in a wavelength region that is complementary to reflectance spectroscopy. The essence of the completed research was to analyze TES data in the context of reflectance data obtained by the French ISM imaging spectrometer experiment in 1989. This approach increased our understanding of the complementary nature of these wavelength regions for mineralogic determinations using actual observations of the martian surface. The research effort focused on three regions of scientific importance: Syrtis Major-Isidis Basin, Oxia Palus-Arabia, and Valles Marineris. In each region distinct spatial variations related to reflectance, and in derived mineralogic information and interpreted compositional units were analyzed. In addition, specific science questions related to the composition of volcanics and crustal evolution, soil compositions and pedogenic processes, and the relationship between pristine lithologies and weathering provided an overall science-driven framework for the work. The detailed work plan involved colocation of TES and ISM data, extraction of reflectance and emissivity spectra from areas of known reflectance variability, and quantitative analysis using factor analysis and statistical techniques to determine the degree of correspondence between these different wavelength regions. Identified coherent variations in TES spectroscopy were assessed against known atmospheric effects to validate that the variations are due to surface properties. With this new understanding of reflectance and emission spectroscopy, mineralogic interpretations were derived and applied to the science objectives of the three regions.

Boyce, Joseph↗
NASA NTRS2007

Mars Exploration Rover Pancam Multispectral Imaging of Rocks, Soils, and Dust at Gusev Crater and Meridiani Planum

Multispectral imaging from the Panoramic Camera (Pancam) instruments on the Mars Exploration Rovers Spirit and Opportunity has provided important new insights about the geology and geologic history of the rover landing sites and traverse locations in Gusev crater and Meridiani Planum. Pancam observations from near-UV to near-IR wavelengths provide limited compositional and mineralogic constraints on the presence abundance, and physical properties of ferric- and ferrous-iron bearing minerals in rocks, soils, and dust at both sites. High resolution and stereo morphologic observations have also helped to infer some aspects of the composition of these materials at both sites. Perhaps most importantly, Pancam observations were often efficiently and effectively used to discover and select the relatively small number of places where in situ measurements were performed by the rover instruments, thus supporting and enabling the much more quantitative mineralogic discoveries made using elemental chemistry and mineralogy data. This chapter summarizes the major compositionally- and mineralogically-relevant results at Gusev and Meridiani derived from Pancam observations. Classes of materials encountered in Gusev crater include outcrop rocks, float rocks, cobbles, clasts, soils, dust, rock grindings, rock coatings, windblown drift deposits, and exhumed whitish/yellowish salty soils. Materials studied in Meridiani Planum include sedimentary outcrop rocks, rock rinds, fracture fills, hematite spherules, cobbles, rock fragments, meteorites, soils, and windblown drift deposits. This chapter also previews the results of a number of coordinated observations between Pancam and other rover-based and Mars-orbital instruments that were designed to provide complementary new information and constraints on the mineralogy and physical properties of martian surface materials.

Bell, J. F., III↗
NASA NTRS2010

FIB-NanoSIMS-TEM Coordinated Study of a Wark-Lovering Rim in a Vigarano Type A CAI

Wark-Lovering (WL) rims are thin multi layered mineral sequences that surround most Ca, Al-rich inclusions (CAIs). Unaltered WL rims are composed of the same primary high temperature minerals as CAIs, such as melilite, spinel, pyroxene, hibonite, perovskite, anorthite and olivine. It is still unclear whether the rim minerals represent a different generation formed by a separate event from their associated CAIs or are a byproduct of CAI formation. Several models have been proposed for the origins of WL rims including condensation, flashheating, reaction of a CAI with a Mg-Si-rich reservoir (nebular gas or solid); on the basis of mineralogy, abundances of trace elements, O and Mg isotopic studies. Detailed mineralogical characterizations of WL rims at micrometer to nanometer scales have been obtained by TEM observations, but so far no coordinated isotopic - mineralogical studies have been performed. Thus, we have applied an O isotopic imaging technique by NanoSIMS 50L to investigate heterogeneous distributions of O isotopic ratios in minerals within a cross section of a WL rim prepared using a focused ion beam (FIB) instrument. After the isotopic measurements, we determine the detailed mineralogy and microstructure of the same WL FIB section to gain insight into its petrogenesis. Here we present preliminary results from O isotopic and elemental maps by NanoSIMS and mineralogical analysis by FE-SEM of a FIB section of a WL rim in the Vigarano reduced CV3 chondrite.

Cai, A.↗
NASA NTRS2009

Proceedings of the 40th Lunar and Planetary Science Conference

The 40th Lunar and Planetary Science Conference included sessions on: Phoenix: Exploration of the Martian Arctic; Origin and Early Evolution of the Moon; Comet Wild 2: Mineralogy and More; Astrobiology: Meteorites, Microbes, Hydrous Habitats, and Irradiated Ices; Phoenix: Soil, Chemistry, and Habitability; Planetary Differentiation; Presolar Grains: Structures and Origins; SPECIAL SESSION: Venus Atmosphere: Venus Express and Future Missions; Mars Polar Caps: Past and Present; SPECIAL SESSION: Lunar Missions: Results from Kaguya, Chang'e-1, and Chandrayaan-1, Part I; 5 Early Nebula Processes and Models; SPECIAL SESSION: Icy Satellites of Jupiter and Saturn: Cosmic Gymnasts; Mars: Ground Ice and Climate Change; SPECIAL SESSION: Lunar Missions: Results from Kaguya, Chang'e-1, and Chandrayaan-1, Part II; Chondrite Parent-Body Processes; SPECIAL SESSION: Icy Satellites of Jupiter and Saturn: Salubrious Surfaces; SNC Meteorites; Ancient Martian Crust: Primary Mineralogy and Aqueous Alteration; SPECIAL SESSION: Messenger at Mercury: A Global Perspective on the Innermost Planet; CAIs and Chondrules: Records of Early Solar System Processes; Small Bodies: Shapes of Things to Come; Sulfur on Mars: Rocks, Soils, and Cycling Processes; Mercury: Evolution and Tectonics; Venus Geology, Volcanism, Tectonics, and Resurfacing; Asteroid-Meteorite Connections; Impacts I: Models and Experiments; Solar Wind and Genesis: Measurements and Interpretation; Mars: Aqueous Processes; Magmatic Volatiles and Eruptive Conditions of Lunar Basalts; Comparative Planetology; Interstellar Matter: Origins and Relationships; Impacts II: Craters and Ejecta Mars: Tectonics and Dynamics; Mars Analogs I: Geological; Exploring the Diversity of Lunar Lithologies with Sample Analyses and Remote Sensing; Chondrite Accretion and Early History; Science Instruments for the Mars Science Lander; . Martian Gullies: Morphology and Origins; Mars: Dunes, Dust, and Wind; Mars: Volcanism; Early Solar System Chronology; Seek Out and Explore: Upcoming and Future Missions; Mars: Early History and Impact Processes; Mars Analogs II: Chemical and Spectral; Achondrites and their Parent Bodies; and Planning for Future Exploration of the Moon The poster sessions were: Lunar Missions: Results from Kaguya, Chang'e-1, and Chandrayaan-1; LRO and LCROSS; Geophysical Analysis of the Lunar Surface and Interior; Remote Observation and Geologic Mapping of the Lunar Surface; Lunar Spectroscopy; Venus Geology, Geophysics, Mapping, and Sampling; Planetary Differentiation; Bunburra and Buzzard Coulee: Recent Meteorite Falls; Meteorites: Terrestrial History; CAIs and Chondrules: Records of Early Solar System Processes; Volatile and Organic Compounds in Chondrites; Crashing Chondrites: Impact, Shock, and Melting; Ureilite Studies; Petrology and Mineralogy of the SNC Meteorites; Martian Meteorites; Phoenix Landing Site: Perchlorate and Other Tasty Treats; Mars Polar Atmospheres and Climate Modeling; Mars Polar Investigations; Mars Near-Surface Ice; Mars: A Volatile-Rich Planet; Mars: Geochemistry and Alteration Processes; Martian Phyllosilicates: Identification, Formation, and Alteration; Astrobiology; Instrument Concepts, Systems, and Probes for Investigating Rocks and Regolith; Seeing is Believing: UV, VIS, IR, X- and Gamma-Ray Camera and Spectrometer Instruments; Up Close and Personal: In Situ Analysis with Laser-Induced Breakdown Spectroscopy and Mass Spectrometry; Jupiter and Inscrutable Io; Tantalizing Titan; Enigmatic Enceladus and Intriguing Iapetus; Icy Satellites: Cryptic Craters; Icy Satellites: Gelid Geology/Geophysics; Icy Satellites: Cool Chemistry and Spectacular Spectroscopy; Asteroids and Comets; Comet Wild 2: Mineralogy and More; Hypervelocity Impacts: Stardust Models, LDEF, and ISPE; Presolar Grains; Early Nebular Processes: Models and Isotopes; Solar Wind and Genesis: Measurements and Interpretation; Education and Public Outreach; Mercury; Pursuing Lunar Exploration; Sources and Eruptionf Lunar Basalts; Chemical and Physical Properties of the Lunar Regolith; Lunar Dust and Transient Surface Phenomena; Lunar Databases and Data Restoration; Meteoritic Samples of the Moon; Chondrites, Their Clasts, and Alteration; Achondrites: Primitive and Not So Primitive; Iron Meteorites; Meteorite Methodology; Antarctic Micrometeorites; HEDs and Vesta; Dust Formation and Transformation; Interstellar Organic Matter; Early Solar System Chronology; Comparative Planetology; Impacts I: Models and Experiments; Impacts II: Craters and Ejecta; Mars: Volcanism; Mars: Tectonics and Dynamics; Martian Stratigraphy: Understanding the Geologic History of Mars Through the Sedimentary Rock Record; Mars: Valleys and Valley Networks; Mars: Aqueous Processes in Valles Marineris and the Southern Highlands; Mars: Aqueous Geomorphology; Martian Gullies: Morphology and Origins; Mars: Dunes, Dust, and Wind; Mars: Remote Sensing; Mars: Geologic Mapping, Photogrammetry, and Cratering; Martian Mineralogy: Constraints from Missions and Laboratory Investigations; Mars Analogs: Chemical and Physical; Mars Analogs: Sulfates and Sulfides; Missions: Approaches, Architectures, Analogs, and Actualities; Not Just Skin Deep: Electron Microscopy, Heat Flow, Radar, and Seismology Instruments and Planetary Data Systems, Techniques, and Interpretation.

Source record↗
NASA NTRS2017

Surveying Clay Mineral Diversity in the Murray Formation, Gale Crater, Mars

The CheMin XRD instrument aboard Mars Science Laboratory (MSL) has documented clay minerals in various drill samples during its traverse of Gale Crater's floor and ascent of Mt. Sharp. The most recent samples, named Marimba, Quela and Sebina were acquired from the Murray Formation in the Murray Buttes region of lower Mt. Sharp. Marimba and Quela come from a approx. 30 m package of finely laminated lacustrine mudstones. Sebina comes from an overlying package of heterolithic mudstone-sandstones. Clay minerals make up approx.15-25 wt.% of the bulk rock with similar contributions to XRD patterns in all three samples. Broad basal reflections at approx. 10deg 2(theta) CoK(alpha) indicate the presence of 2:1 group clay minerals. The 02(lambda) clay mineral band lies at approx. 22.9deg 2(theta), a region typically occupied by Fe-bearing dioctahedral 2:1 clay minerals like nontronite or Fe-illite. The low humidity within the CheMin instrument, which is open to the martian atmosphere, promotes loss of interlayer H2O and collapse of smectite interlayers making them difficult to distinguish from illites. However, based on the low K content of the bulk samples, it appears that smectitic clay minerals are dominant. Peak dehydroxylation of the Marimba sample measured by the SAM instrument on MSL occurred at 610C and 780C. Fe-bearing smectites are not consistent with these dehydroxylation temperatures. Thus, we suggest that a mixture of dioctahedral and trioctahedral smectite phases are present giving the appearance of intermediate octahedral occupancy in XRD. Dioctahedral smectites have not previously been reported in Gale Crater by MSL. Earlier in the mission, relatively clay mineral rich samples (approx. 20 wt.%) from lacustrine mudstones in Yellowknife Bay (YKB) were found to contain ferrian saponites. It is proposed that YKB saponites formed via isochemical aqueous alteration of detrital olivine close to the time of sediment deposition, under anoxic to poorly oxidizing conditions. In terrestrial settings where alteration sequences of basaltic rocks or sediments are observed, first-stage alteration clay minerals are typically trioctahedral smectite species, as reported from YKB. In later alteration stages trioctahedral clay minerals are replaced by dioctahedral clays as a result of removal and/or oxidation of Fe2+ and Mg. Observed changes in clay mineralogy between YKB and Murray Buttes samples correspond with differences in bulk mineralogy, including: 1) a transition from magnetite to hematite as the main Fe-oxide, 2) increasing abundances of Ca-sulfates and 3) a reduction in the quantity of reactive mafic minerals. This mineralogical change indicates an increasing degree of aqueous alteration and oxidation of mafic detritus in the upper part of the Murray Formation. These results broaden the spectrum of mineralogical facies documented by MSL. Together sedimentology and mineralogy indicate a long-lasting, dynamic fluvial-lacustrine system encompassing a range aqueous geochemical processes under varying redox conditions. Future work is needed to unravel the influence of global and local controls on the range of ancient conditions observed at Gale Crater.

MSL↗
NASA NTRS2018

Potential Mercurian Analogues: Aubrite and Enstatite Chondrite Impact Melt Meteorites

The MESSENGER (MErcury Surface Space ENvironment GEochemistry and Ranging Spacecraft) mission provided new data that have helped us better constrain the surficial mineralogy and composition of Mercury. Mercury has an extremely low oxygen fugacity (f O2) (Iron Wustite (IW) -7.3 to IW -2.6), and at these unique conditions, elements, which usually exhibit lithophile behavior on Earth, can exhibit chalcophile or siderophile behavior on Mercury. No samples have been returned from Mercury; therefore, we must study candidate meteorite analogs to better understand the formation conditions of minerals inferred to be present at the Mercurian surface and Mercurian magmatic processes. In this study, we present a comprehensive analysis of a representative suite of eight aubrites and four enstatite chondrite impact melts (ECIM), which both have a similar f O2 to Mercury, and contain exotic sulfides that have been inferred to be present at the Mercurian surface. These characteristics allow us to assess their relevance for understanding the mineralogy and magmatic processes of Mercury. The ECIM were previously classified as aubrites, but we show that they are actually ECIM with a potential EH (high enstatite) parent body origin due to the presence of niningerite, Si-enriched kamacite, and uniform Ni in schreibersite. We propose that, with respect to the aubrites, the ECIM represent an ideal candidate for Mercurian studies due to their mineralogy and modal mineralogy. Compared to the aubrites, the ECIM samples do not contain forsterite or diopside, show a poorer sulfide diversity, contain graphite, and have a higher volume percentage of metal phases. Although the Mercurian surface contains forsterite and diopside, graphite and a similar amount of metal and sulfides as seen in the ECIM are inferred to be present on Mercury. According to the calculated normative Mercurian mineralogy, both candidate meteorites are most analogous to the Caloris Basin and Northern Plains Lower Mg regions.

Wilbur, Zoe E.↗
NASA NTRS2020

X-ray Amorphous Components of Antarctica Dry Valley Soils: Weathering Implications for Mars

The Antarctic Dry Valleys (ADV) comprise the largest ice-free region of Antarctica. Precipitation usually occurs as snow, relative humidity is frequently low, and mean annual temperatures are about -20°C [1]. Substantial work has focused on soil formation in the ADVs [2], however, little work has focused on the mineralogy of secondary alteration phases. The dominant weathering process in the ADV region is physical weathering, however, chemical weathering has been well documented [3]. The occurrence of chemical weathering processes are suggested by the presence of clay minerals and iron and titanium oxides in soil. Previously we have investigated soils from two sites in the ADV’s and have shown evidence of chemical weathering by the presence of clay minerals (vermiculite, smectite), short-range ordered (SRO) and/or X-ray amorphous materials, and Fe- and Tioxides as well as the presence of discrete calcite crystals [4, 5]. The Chemistry and Mineralogy (CheMin) instrument onboard the Mars Curiosity rover has detected abundant amounts (approx. 25-30 wt. %) of X-ray amorphous materials in a windblown deposit or “soil” (Rocknest) and in a sedimentary rocks [6,7,8]. The occurrence of large amounts of X-ray amorphous materials in Mars sediments is surprising because these materials are usually present in small quantities in terrestrial environments. The objective of this study is to further characterize the chemistry and mineralogy, specifically the secondary alteration mineralogy and the presence of X-ray amorphous material, of soils from two sites we have previously studied, a subxerous soil in Taylor Valley, and an ultraxerous soil in University Valley. While the chemical alteration processes and mineralogy of the ADV has been documented previously, there has been limited discussion on the occurrence and formation of X-ray amorphous and SRO materials in Antarctica soils. The process of aqueous alteration in the ADVs may have implications for pedogenic processes on Mars, and may lead to a better understanding to the abundance of amorphous material found in sediments in Gale crater.

Quinn, J. E.↗
NASA NTRSDate not supplied

Aqueous alteration of Cb-type asteroid Ryugu

The samples from the asteroid Ryugu, which returned to Earth in the winter of 2020 [1], were stored under pure Nitrogen conditions at the Extraterrestrial Materials Curation Center of ISAS. After basic description [2-3], they were distributed to six initial analysis teams in Japan in June 2021. The initial analysis "Stone" team, which was responsible for the analysis of coarse particles (>1 mm in size), consisted of about 150 scientists from Japan and abroad, and conducted a series of analyses We analyzed sixteen coarse Ryugu particles 1 ~ 8 mm in size: six from the 1st touch-down site and ten from the 2nd touch-down site. Individual coarse samples were cut by Xe-FIB or wire-saw to expose particular objects or textures to be exposed on the surface based on 3D structure and element distribution obtained by synchrotron X-ray CT analysis and XRF analysis, respectively. FE-SEM/EDS and FE-EPMA/WDS analysis were made on all polished sections. TEM observation of many FIB sections was made to see microstructures and to compare with carbonaceous chondrites. Many other analyses were carried out to characterize mineralogical and compositional properties and summary of the analysis procedures is described in [4]. X-ray CT analysis showed that all sixteen Ryugu particles are composed of fine-grained material, with no chondrules and CAIs larger than 100 μm in size. FE-EPMA observation showed that Ryugu samples are breccias, consisting of many small rock fragments of different compositions, lithologies, and histories. The most common lithology includes Mg-rich saponite and serpentine, dolomite, magnesite, hydroxyapatite, pyrrhotite, and magnetite as main constituents. The mineralogy of this major lithology supports the classification of Ryugu samples as CI chondrites, which experienced extensive aqueous alteration in Ryugu’s parent asteroid. Based on the obtained mineralogical properties, we performed chemical modeling of aqueous alteration of Ryugu’s parent asteroid [5]. Numerical simulations [6-8] to reproduce thermal history and impact-induced destruction of the Ryugu’s parent asteroid were also carried out using mineralogical and physical properties of the Ryugu samples. In the talk, I would like to explain the conditions of aqueous alteration occurred in the parent asteroid of Ryugu in order to show how the water in the asteroid changed the mineralogy and chemistry of the nebular dust.

T. Nakamura↗
DOE OSTI2020

Spectral, Compositional, and Physical Properties of the Upper Murray Formation and Vera Rubin Ridge, Gale Crater, Mars

During 2018 and 2019, the Mars Science Laboratory Curiosity rover investigated the chemistry, morphology, and stratigraphy of Vera Rubin ridge (VRR). Using orbital data from the Compact Reconnaissance Imaging Spectrometer for Mars, scientists attributed the strong 860 nm signal associated with VRR to the presence of red crystalline hematite. However, Mastcam multispectral data and CheMin X-ray diffraction (XRD) measurements show that the depth of the 860 nm absorption is negatively correlated with the abundance of red crystalline hematite, suggesting that other mineralogical or physical parameters are also controlling the 860 nm absorption. Here, we examine Mastcam and ChemCam passive reflectance spectra from VRR and other locations to link the depth, position, and presence or absence of iron-related mineralogic absorption features to the XRD-derived rock mineralogy. Correlating CheMin mineralogy to spectral parameters showed that the ~860 nm absorption has a strong positive correlation with the abundance of ferric phyllosilicates. New laboratory reflectance measurements of powdered mineral mixtures can reproduce trends found in Gale crater. We hypothesize that variations in the 860 nm absorption feature in Mastcam and ChemCam observations of VRR materials are a result of three factors: (1) variations in ferric phyllosilicate abundance due to its ~800–1,000 nm absorption; (2) variations in clinopyroxene abundance because of its band maximum at ~860 nm; and (3) the presence of red crystalline hematite because of its absorption centered at 860 nm. We also show that relatively small changes in Ca-sulfate abundance is one potential cause of the erosional resistance and geomorphic expression of VRR.

58 GEOSCIENCES↗
DOE OSTI2020

EXPERIMENTAL EVALUATION OF ULTRASONIC VELOCITIES AND ANISOTROPY IN THE TUSCALOOSA MARINE SHALE FORMATION

Tuscaloosa Marine Shale (TMS) formation is a clay- and organic-rich emerging shale play with a considerable amount of hydrocarbon resources. Despite the substantial potential, there have been only a few wells drilled and produced in the formation over the recent years. The analyzed TMS samples contain an average of 50 wt% total clay, 27 wt% quartz and 14 wt% calcite and the mineralogy varies considerably over the small intervals. The high amount of clay leads to pronounced anisotropy and the frequent changes in mineralogy result in the heterogeneity of the formation. We studied the compressional (V P ) and shear-wave (V S ) velocities to evaluate the degree of anisotropy and heterogeneity, which impact hydraulic fracture growth, borehole instabilities, and subsurface imaging. The ultrasonic measurements of P- and S-wave velocities from five TMS wells are the best fit to the linear relationship with R 2 = 0.84 in the least-squares criteria. We observed that TMS S-wave velocities are relatively lower when compared to the established velocity relationships. Most of the velocity data in bedding-normal direction lie outside constant V P /V S lines of 1.6–1.8, a region typical of most organic-rich shale plays. For all of the studied TMS samples, the S-wave velocity anisotropy exhibits higher values than P-wave velocity anisotropy. In the samples in which the composition is dominated by either calcite or quartz minerals, mineralogy controls the velocities and V P /V S ratios to a great extent. Additionally, the organic content and maturity account for the velocity behavior in the samples in which the mineralogical composition fails to do so. The results provide further insights into TMS Formation evaluation and contribute to a better understanding of the heterogeneity and anisotropy of the play.

Geochemistry & Geophysics↗
DOE OSTI2026

Microwave-Assisted Hydrogen Generation from Hydrocarbon-Bearing Reservoir Rocks: Stage-Dependent Thermal Runaway and In-Situ Carbonate Engineering

Microwave-assisted hydrogen generation from hydrocarbon-bearing reservoir rocks is strongly influenced by mineralogy, methane activation, carbonate reactions, and thermal runaway behavior. This study investigates a new approach in which carbonate phases are generated in-situ through the reaction of internally produced CO2 with Ca(OH)2 under microwave heating conditions. The objective is to evaluate how rock mineralogy, methane injection, and Ca(OH)2 addition influence hydrogen generation, carbon redistribution, and stage-dependent reaction pathways during microwave exposure. Microwave heating experiments were conducted using Permian Basin reservoir rocks under three experimental conditions: rock-only experiments under Ar atmosphere, CH4–Ar experiments without additive, and CH4–Ar experiments containing 5 wt% Ca(OH)2. Methane-assisted experiments were performed under continuous injection of 30 standard cubic centimeters per minute (sccm) CH4 and 30 sccm Ar. Based on thermal runaway behavior, each experiment was divided into three operational stages: Before Thermal Runaway (BR), After Thermal Runaway–Decrease in Microwave Power (ARD), and After Thermal Runaway– Increase in Microwave Power (ARI). Temperature and gas composition were continuously monitored throughout the experiments. The rock-only experiments demonstrated that hydrogen generation can occur intrinsically from hydrocarbon-bearing rocks under microwave heating, even without externally injected methane. However, hydrogen production did not correlate solely with kerogen content, indicating that mineralogy strongly influences hydrogen-generation pathways. Correlation analyses suggested that kerogen decomposition initially generated CH4, CO, and CO2, followed by secondary hydrocarbon reactions associated with H2 and C2 hydrocarbon formation. Methane-assisted experiments substantially increased hydrogen production; however, identical methane injection rates produced significantly different hydrogen yields among the rock samples, confirming that mineralogical composition controls methaneconversion behavior under microwave heating conditions. The addition of Ca(OH)2 significantly altered carbon evolution behavior in a stage-dependent manner. During the BR stage, Ca(OH)2 reduced gas-phase CO2 production, particularly in carbonate-rich rocks, indicating favorable conditions for in-situ carbonation and carbonate deposition prior to extensive thermal decomposition. The suppression of CO2 during BR became more pronounced with increasing carbonate content of the rock system. After thermal runaway, carbonate-containing systems exhibited enhanced hydrogen generation behavior, suggesting that carbonatederived mineral transformations and carbonate-mediated reactions contribute to high-temperature hydrogen-generation pathways. In carbonate-poor rocks, Ca(OH)2 addition enabled simultaneous URTeC 4493775 2 enhancement of hydrogen production and partial suppression of CO2 release during the post-runaway stages. Overall, the results demonstrate that microwave-assisted hydrogen generation is governed by dynamically evolving interactions among kerogen decomposition, methane activation, mineral transformations, carbonate formation/decomposition, and thermal runaway behavior. This work introduces in-situ carbonate engineering with Ca(OH)2 as a strategy for coupling hydrogen generation with partial insitu carbon management under microwave heating conditions.

03 NATURAL GAS↗
DOE OSTI2021

Patterns of Element Incorporation in Calcium Carbonate Biominerals Recapitulate Phylogeny for a Diverse Range of Marine Calcifiers

Elemental ratios in biogenic marine calcium carbonates are widely used in geobiology, environmental science, and paleoenvironmental reconstructions. It is generally accepted that the elemental abundance of biogenic marine carbonates reflects a combination of the abundance of that ion in seawater, the physical properties of seawater, the mineralogy of the biomineral, and the pathways and mechanisms of biomineralization. Here we report measurements of a suite of nine elemental ratios (Li/Ca, B/Ca, Na/Ca, Mg/Ca, Zn/Ca, Sr/Ca, Cd/Ca, Ba/Ca, and U/Ca) in 18 species of benthic marine invertebrates spanning a range of biogenic carbonate polymorph mineralogies (low-Mg calcite, high-Mg calcite, aragonite, mixed mineralogy) and of phyla (including Mollusca, Echinodermata, Arthropoda, Annelida, Cnidaria, Chlorophyta, and Rhodophyta) cultured at a single temperature (25°C) and a range of p CO 2 treatments (ca. 409, 606, 903, and 2856 ppm). This dataset was used to explore various controls over elemental partitioning in biogenic marine carbonates, including species-level and biomineralization-pathway-level controls, the influence of internal pH regulation compared to external pH changes, and biocalcification responses to changes in seawater carbonate chemistry. The dataset also enables exploration of broad scale phylogenetic patterns of elemental partitioning across calcifying species, exhibiting high phylogenetic signals estimated from both uni- and multivariate analyses of the elemental ratio data (univariate: λ = 0–0.889; multivariate: λ = 0.895–0.99). Comparing partial R 2 values returned from non-phylogenetic and phylogenetic regression analyses echo the importance of and show that phylogeny explains the elemental ratio data 1.4–59 times better than mineralogy in five out of nine of the elements analyzed. Therefore, the strong associations between biomineral elemental chemistry and species relatedness suggests mechanistic controls over element incorporation rooted in the evolution of biomineralization mechanisms.

58 GEOSCIENCES↗