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At least 55 records · Page 3

In-Situ and Experimental Evidence for Acidic Weathering of Rocks and Soils on Mars

Experimental data for alteration of synthetic Martian basalts at pH=0-1 indicate that chemical fractionations at low pH are vastly different from those observed during terrestrial weathering. Rock analyses from Gusev crater are well described by the relationships apparent from low pH experimental alteration data. A model for rock surface alteration is developed which indicates that a leached alteration zone is present on rock surfaces at Gusev. This zone is not chemically fractionated to a large degree from the underlying rock interior, indicating that the rock surface alteration process has occurred at low fluid-to-rock ratio. The geochemistry of natural rock surfaces analyzed by APXS is consistent with a mixture between adhering soil/dust and the leached alteration zone. The chemistry of rock surfaces analyzed after brushing with the RAT is largely representative of the leached alteration zone. The chemistry of rock surfaces analyzed after grinding with the RAT is largely representative of the interior of the rock, relatively unaffected by the alteration process occurring at the rock surface. Elemental measurements from the Spirit, Opportunity, Pathfinder and Viking 1 landing sites indicate that soil chemistry from widely separated locations is consistent with the low-pH, low fluid to rock ratio alteration relationships developed for Gusev rocks. Soils are affected principally by mobility of FeO and MgO, consistent with alteration of olivine-bearing basalt and subsequent precipitation of FeO and MgO bearing secondary minerals as the primary control on soil geochemistry.

Hurowitz, J. A.↗

Effect of oxidative breakers on organic matter degradation, contaminant mobility and critical mineral release during shale-fracturing fluid interactions in the Marcellus Shale

Oil and gas production from organic-rich shale formations has become viable through advancements in multistage hydraulic fracturing. However, fluctuations in oil and gas prices, coupled with the sharp decline in gas production after the initial days of fracturing operations, drive operators to devise strategies for enhancing hydrocarbon production. The use of highly reactive fracturing fluids that include strong oxidizing agents, also known as breakers, can potentially increase well productivity. The oxidative breakers are used to reduce the viscosity of gel-based fluids after the proppant is transported into fracture zones of the target formation. These breakers can also degrade the organic matter, enhancing the release of hydrocarbons. However, chemical byproducts generated by the interaction of oxidative breakers with the shale matrix have not been extensively studied. Here, this study investigated the fluid-rock interactions between Marcellus Shale and synthetic hydraulic fracturing fluid (HFF) solutions comprising three different oxidative breakers, i.e., ammonium persulfate, sodium bromate, and sodium hypochlorite, commonly used in the Appalachian Basin, USA. Our results demonstrate that the type of oxidizing breakers used in the HFF controlled the type and amount of volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs) produced. In all HFF reacted effluents, we observed the transformation of VOCs and the presence of organic acids in variable amounts. However, effluents from HFF containing sodium bromate and sodium hypochlorite breakers showed the presence of several halogenated organic compounds. Changes in major ions and mineralogy indicate that carbonate dissolution and barite precipitation were ubiquitous in all shale reacted effluents. Our results also demonstrate that the addition of oxidative breakers increased the concentration of several major and trace elements in the effluents. These elements fall under the critical mineral (CM) or critical element category due to their high demand in emerging technologies and susceptibility to supply chain disruption due to variety of factors. However, before oxidative breakers can be used at a larger field scale to enhance the release and recovery of CM and hydrocarbons, a better understanding is required of the potential environmental impacts associated with the generation and transformation of contaminants during breaker-fluid-rock interaction.

54 ENVIRONMENTAL SCIENCES↗

Dynamic risk assessment for geologic CO 2 sequestration

At a geologic CO 2 sequestration (GCS) site, geologic uncertainty usually leads to large uncertainty in the predictions of properties that influence metrics for leakage risk assessment, such as CO 2 saturations and pressures in potentially leaky wellbores, CO 2 /brine leakage rates, and leakage consequences such as changes in drinking water quality in groundwater aquifers. The large uncertainty in these risk-related system properties and risk metrics can lead to over-conservative risk management decisions to ensure safe operations of GCS sites. The objective of this work is to develop a novel approach based on dynamic risk assessment to effectively reduce the uncertainty in the predicted risk-related system properties and risk metrics. We demonstrate our framework for dynamic risk assessment on two case studies: a 3D synthetic example and a synthetic field example based on the Rock Springs Uplift (RSU) storage site in Wyoming, USA. Results show that the U.S. National Risk Assessment Partnership’s Open Source Integrated Assessment Model (NRAP-Open-IAM) coupled with a conformance evaluation can be used to effectively quantify and reduce the uncertainty in the predictions of risk-related system properties and risk metrics in GCS.

58 GEOSCIENCES↗

Viscosity of lunar lavas

Synthetic silicate liquid viscosity with lunar rock composition compared with volcanic rock on earth

Mcbirney, A. R.↗

Nanofabrication of synthetic nanoporous geomaterials: from nanoscale-resolution 3D imaging to nano-3D-printed digital (shale) rock

Abstract Advances in imaging have made it possible to view nanometer and sub-nanometer structures that are either synthesized or that occur naturally. It is believed that fluid dynamic and thermodynamic behavior differ significantly at these scales from the bulk. From a materials perspective, it is important to be able to create complex structures at the nanometer scale, reproducibly, so that the fluid behavior may be studied. New advances in nanoscale-resolution 3D-printing offer opportunities to achieve this goal. In particular, additive manufacturing with two-photon polymerization allows creation of intricate structures. Using this technology, a creation of the first nano-3D-printed digital (shale) rock is reported. In this paper, focused ion beam-scanning electron microscopy (FIB-SEM) nano-tomography image dataset was used to reconstruct a high-resolution digital rock 3D model of a Marcellus Shale rock sample. Porosity of this 3D model has been characterized and its connected/effective pore system has been extracted and nano-3D-printed. The workflow of creating this novel nano-3D-printed digital rock 3D model is described in this paper.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Time-lapse seismic inversion for CO 2 saturation with SeisCO2Net: An application to Frio-II site

Seismic monitoring of geological CO 2 storage (GCS) involves highly nonlinear seismic inversion and petrophysical inversion, making it challenging to estimate CO 2 volume efficiently and detect possible early CO 2 leakages. Deep learning (DL) using convolutional neural networks (CNNs) has shown promise in solving highly nonlinear seismic inversion problems. However, direct estimation of CO 2 plume extent/saturation from time-lapse seismic gathers using DL is still underexplored, with no reported field applications to date. The investigation of field data is primarily hindered by scarcity of field data for neural network training. Other obstacles include highly nonlinear seismic-petrophysics inverse relationship, and presence of noise in field seismic data. We introduce SeisCO2Net, a deep CNN that predicts CO 2 saturation maps directly from time-lapse full waveform shot gathers. For training, we use site-specific geological information, fluid flow physics, rock physics, and seismic modeling to generate synthetic datasets that closely resemble the CO 2 storage site. Synthetic tests show promising results, inspiring us to apply SeisCO2Net's trained weights on field data collected at Frio-II GCS site by leveraging transfer learning principles. As reference, we compare SeisCO2Net's predicted CO 2 saturation maps with results obtained from physics-based inversion. Our analyses show both methods display similar CO 2 plume shapes, reasonable CO 2 plume characteristics, and comparable saturation values. Our results suggest pre-training CNNs on physics-informed synthetic datasets and then applying the learned weights to field data is a viable approach to estimating field CO 2 saturation. This method effectively addresses the scarcity of field training data, thus encouraging the feasibility of long-term GCS monitoring.

58 GEOSCIENCES↗

Formation of Fe/mg Smectite Under Acidic Conditions from Synthetic Adirondack Basaltic Glass: an Analog to Fe/mg Smectite Formation on Mars

Smectite has been detected as layered material hundreds of meters thick, in intracrater depositional fans, in plains sediments, and deposits at depth on Mars. If early Mars hosted a dense CO2 atmosphere, then extensive carbonate should have formed in the neutral/alkaline conditions expected for smectite formation. However, large carbonate deposits on Mars have not been discovered. Instead of neutral to moderately alkaline conditions, early Mars may have experienced mildly acidic conditions that allowed for Fe/Mg smectite formation but prevented widespread carbonate formation. The objective of this work is to demonstrate that Fe(II)/Mg saponite and nontronite can form in mildly acidic solutions (e.g., pH 4). Synthetic basaltic glass (< 53 microns) of Adirondack rock class composition was exposed to pH 4 (acetic acid buffer) and N2 purged (anoxic) solutions amended with 0 and 10 mM Mg or Fe(II). Basaltic glass in these solutions was heated to 200 C in batch reactors for 1, 7, and 14 days. X-ray diffraction analysis of reacted materials detected the presence of phyllosilicates as indicated by a approx. 15.03-15.23Angstroms (001) peak. Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. Trioctahedral saponite was confirmed by the presence of a 4.58 to 4.63 Angstroms (02l) and 1.54Angstroms (060) peaks. Saponite concentration was highest, as indicated by XRD peak intensity, in the 10 mM Mg treatment followed by the 0 mM and then 10 mM Fe(II) treatments. This order of sapontite concentration suggests that Fe(II) additions may have a role in slowing the kinetics of saponite formation relative to the other treatments. Nontronite synthesis was attempted by exposing Adirondack basaltic glass to pH 4 oxic solutions (without N2 purge) at 200 C for 14 days. X-ray diffraction analysis indicated that mixtures of trioctahedral (saponite) and dioctahedral (nontronite) may have formed in these experiments based on the 02l and 060 peaks. Moessbauer analysis coupled with future experiments are planned to verify if nontronite can be formed under mildly acidic and oxic conditions. Results of this work demonstrate that acidic conditions could have occurred on an early Mars, which allowed for smectite formation but inhibited carbonate formation.

Sutter, B.↗

CMPO-Functionalized Silica Sorbents for pH-Tunable Separation and Enrichment of Rare-Earth Elements from Environmental Matrices

Rare-earth elements (REEs) are crucial in many applications, yet mutual separation is challenging due to their similar chemical behavior. Octylphenyl- N,N-diisobutyl carbamoyl methyl phosphine oxide (CMPO) is an organophosphorus ligand originally developed for extracting actinides and lanthanides from spent nuclear fuel. Here, we report a pH-tunable CMPOfunctionalized silica sorbent for selective REE separation from complex aqueous matrices. A CMPO-associated silica gel sorbent was synthesized and characterized by Brunauer−Emmett−Teller (BET) surface area, scanning electron microscopy, and X-ray photoelectron spectroscopy to confirm the surface functionalization and binding behavior. Sorbent performance was evaluated by using a synthetic 46- element solution and a real phosphate rock fertilizer leachate. Notably, REEs were successfully eluted with ultrapure water, demonstrating reversible desorption controlled by pH adjustment. Packed-bed column studies increased the REE mass fraction from 3.6% to 64% (20-fold enrichment), with up to 30-fold enrichment of neodymium. The adsorption process follows the Langmuir isotherm behavior and follows pseudo-second-order kinetics. The uptake capacity of 1 μmol of REEs per 4.2 μmol of CMPO supports the formation of a predominantly 4:1 ligand:rare earth element(III) pseudocomplex. These results demonstrate CMPO-functionalized silica as a selective, water-elutable, and low-chemical-input platform for sustainable REE recovery from environmental and industrial sources.

chelating ligands↗

Measurements of Silicosis Factors in Lunar and Martian Simulants

Simulants are geologically complex materials that are developed to represent the physical and/or compositional characteristics of a planetary surface (e.g., a naturally occurring soil or regolith). There are dozens of commercially available simulants that have been developed over the years; each simulant exhibits unique physical, chemical, and mineralogical characteristics. Simulants are derived from either natural or synthetic sources (i.e., “feedstocks”) of glass, minerals, and rocks. These feedstock components are processed by crushing, pulverizing, melting, etc., and then combined in the appropriate proportions to represent a particular site, surface, or region (e.g., Lunar Highlands Regolith). The process of creating simulants therefore requires the mechanical breakdown and reincorporation of feedstock components which may contain crystalline silica minerals such as quartz, cristobalite, and tridymite. Certain crystalline silica particles of the respirable fraction (<10 μm in diameter) are of great concern; chronic and acute exposure to these respirable crystalline silica (RCS) can lead to permanent damage and scarring of lung tissue, incurable lung diseases (i.e., silicosis), lung cancer, COPD (chronic obstructive pulmonary disease), and kidney disease. Planetary simulants are used extensively as test materials in the in scientific and engineering communities (e.g., testing of dust mitigation technologies, in-situ resource utilization, rover mobility, hardware, soft goods etc.). As such, this assessment was developed to serve as a guide for simulant users, local Safety and Occupational Health professionals, and Industrial Hygienists to evaluate the risk of silicosis across a wide variety of Lunar and Martian simulants. The goal of these works is to ensure that those working with simulant can do so safely and with an informed understanding of potential health risks.

Lunar↗

Measurements of Silicosis Factors in Lunar and Martian Simulants

Simulants are geologically complex materials that are developed to represent the physical and/or compositional characteristics of a planetary surface (e.g., a naturally occurring soil or regolith). There are dozens of commercially available simulants that have been developed over the years; each simulant exhibits unique physical, chemical, and mineralogical characteristics. Simulants are derived from either natural or synthetic sources (i.e., “feedstocks”) of glass, minerals, and rocks. These feedstock components are processed by crushing, pulverizing, melting, etc., and then combined in the appropriate proportions to represent a particular site, surface, or region (e.g., Lunar Highlands Regolith). The process of creating simulants therefore requires the mechanical breakdown and reincorporation of feedstock components which may contain crystalline silica minerals such as quartz, cristobalite, and tridymite. Certain crystalline silica particles of the respirable fraction (<10 μm in diameter) are of great concern; chronic and acute exposure to these respirable crystalline silica (RCS) can lead to permanent damage and scarring of lung tissue, incurable lung diseases (i.e., silicosis), lung cancer, COPD (chronic obstructive pulmonary disease), and kidney disease. Planetary simulants are used extensively as test materials in the in scientific and engineering communities (e.g., testing of dust mitigation technologies, in-situ resource utilization, rover mobility, hardware, soft goods etc.). As such, this assessment was developed to serve as a guide for simulant users, local Safety and Occupational Health professionals, and Industrial Hygienists to evaluate the risk of silicosis across a wide variety of Lunar and Martian simulants. The goal of these works is to ensure that those working with simulant can do so safely and with an informed understanding of potential health risks.

Lunar↗

Lunar and Planetary Science Conference, 10th, Houston, Tex., March 19-23, 1979, Proceedings. Volume 1 - Meteorites and lunar rocks

Papers are presented concerning studies of lunar basalts, highland rocks, and meteorites. Specific topics include the petrology and chemistry of basaltic fragments from Apollo 11 soil; the composition, magma types and petrogenesis of Apollo 17 high-Ti mare basalts; the chemistry and probable origin of Apollo 15 green glass; experimental studies of the partitioning of nickel and chromium into olivine from synthetic basaltic melts; the petrology and geochemistry of pristine highland rocks; the argon isotope age systematics of consortium breccia 73255; magnetite-sulfide-metal complexes in the Allende meteorite; the fractionation of refractory lithophile elements in chondritic meteorites; and the origin and relation to enstatite chondrites of aubrites.

Merrill, R. B.↗

Mobilization of trace metals from caprock and formation rocks at the Illinois Basin – Decatur Project demonstration site under geological carbon dioxide sequestration conditions

One concern for geologic CO 2 sequestration is the potential leakage of CO 2 or CO 2 -saturated brine containing trace metals into overlying aquifers, which poses the risk of adversely affecting underground sources of drinking water. In this work, rock and brine samples collected in the Illinois Basin – Decatur Project (IBDP), a large-scale geological CO 2 sequestration demonstration project in Decatur, Illinois, USA, as well as synthetic brine samples were used to understand the mobilization of trace metals as a result of CO 2 –rock–brine interactions under IBDP-specific conditions (50 °C and 20.6 MPa). Rock sample characterization indicated that, at the IBDP site, trace metal concentrations were greatest in cap rock samples from the Eau Claire Formation, compared with those from formations above and below this Formation. The natural brine samples collected from the Mt. Simon Sandstone reservoir were highly reducing and saline, with trace metal concentrations up to 680 times greater than the U.S. Environmental Protection Agency-prescribed drinking water standards. Batch leaching experiments indicated that both trace metal mobilization from rock and immobilization from the brine occurred when high-pressure CO 2 was introduced into the rock-brine system. The amounts of metals mobilized from the rock generally accounted for <5% of the total metals in the rock, but for some metals, including Ni, Pb, and Tl, up to 63% of the metals in the rock were mobilized to the brine. Leaching of trace metals into synthetic brines was different from that into the natural brine. The results of this study provided current information on the trace element sources and will help in risk simulations and experimental design to further evaluate potential impact of leakage on groundwater quality, which is important for future GCS projects to consider for monitoring and containment assurance purposes.

58 GEOSCIENCES↗

3-D Highway in the Sky

If it were 50 years ago, NASA's contribution to rock and roll could have been more than just the all-astronaut rock band, Max Q, composed of six NASA astronauts, all of whom have flown aboard the Space Shuttle. If it were 50 years ago, a new NASA spinoff technology, Synthetic Vision, would likely have been able to prevent the fateful, small plane crash that killed rock and roll legends Buddy Holly, Ritchie Valens, and The Big Bopper on that stormy night in 1959. Synthetic Vision is a new cockpit display system that helps pilots fly through bad weather, and it has incredible life-saving potential. In 1997, the White House Commission on Aviation Safety and Security created NASA s Aviation Safety and Security Program (AvSSP) with the aim of sounding the depths of NASA s cutting-edge aviation advances and history of successes. The AvSSP decided to use NASA technology to cut the rate of fatal aviation accidents that occur because of lowered visibility and spatial disorientation, common problems that arise in poor weather conditions, in the dark, or with inexperienced pilots.

Source record↗

Rare Earth Element Detection and Quantification in Coal and Rock Mineral Matrices

As global demand for rare earth elements (REEs) increases, maintaining the production and supply chain is critical. Technologies capable of being used in the field and in situ in the subsurface for rapid REE detection and quantification facilitates the efficient mining of known resources and exploration of new and unconventional resources. Laser-induced breakdown spectroscopy (LIBS) is a promising technique for rapid elemental analysis both in the laboratory and in the field. Multiple articles have been published evaluating LIBS for detection and quantification of REEs; however, REEs in their natural deposits have not been adequately studied. In this work, detection and quantification of two REEs, La and Nd, have been studied in both synthetic and natural mineral matrices at concentrations relevant to REE extraction. Measurements were performed on REE-containing rock and coal samples (natural and synthetic) utilizing different LIBS instruments and techniques, specifically a commercial benchtop instrument, a custom benchtop instrument (single- and double-pulse modes), and a custom LIBS probe currently being developed for in situ, subsurface, borehole wall detection and quantification of REEs. Plasma expansion, emission intensity, detection limits, and double-pulse signal enhancement were studied. The limits of detection (LOD) were found to be 10/14 ppm for La and 15/25 ppm for Nd in simulated coal/rock matrices in single-pulse mode. Signal enhancement of 3.5 to 6-fold was obtained with double-pulse mode as compared to single-pulse operation.

La detection↗

Lithologic mapping of silicate rocks using TIMS

Common rock-forming minerals have thermal infrared spectral features that are measured in the laboratory to infer composition. An airborne Daedalus scanner (TIMS) that collects six channels of thermal infrared radiance data (8 to 12 microns), may be used to measure these same features for rock identification. Previously, false-color composite pictures made from channels 1, 3, and 5 and emittance spectra for small areas on these images were used to make lithologic maps. Central wavelength, standard deviation, and amplitude of normal curves regressed on the emittance spectra are related to compositional information for crystalline igneous silicate rocks. As expected, the central wavelength varies systematically with silica content and with modal quartz content. Standard deviation is less sensitive to compositional changes, but large values may result from mixed admixture of vegetation. Compression of the six TIMS channels to three image channels made from the regressed parameters may be effective in improving geologic mapping from TIMS data, and these synthetic images may form a basis for the remote assessment of rock composition.

Gillespie, A. R.↗

Chromium-for-Aluminum Substitution in Synthetic Serpentine

Cr-bearing clay minerals are products of hydrothermal alteration and fluid–rock interactions of ultramafic rocks that form serpentine minerals. Cr is typically observed to substitute for Al in serpentine minerals, but the crystal chemistry and environmental constraints on this substitution are unknown. Here, we synthesized endmember and Cr-substituted amesite, a typical Al-serpentine mineral, via the hydrothermal method. We found that the phase purity highly depends on the pH of the hydrothermal solution, which should be controlled at ~12.7 to avoid the formation of impurity phases. Additionally, amesite can incorporate Cr at a concentration equivalent to ~39.5% substitution of Al. The Cr-free and Cr-substituted amesite are highly defective and contain multiple polytypes, including 6R 2 , 2M 1 , and possibly 2H 2 . However, the relative proportions of these polytypes do not change with increasing chromium substitution.

Al-lizardite↗

Three synthetic lunar glasses

Glasses have been synthesized that have the approximate compositions of lunar rocks 61156, 68415, and 77135, respectively. The glasses have been analyzed by conventional analytical and electron microprobe techniques and have been found to be highly homogeneous. They have been used successfully as electron microprobe standards and for experimental studies of crystallization and solar-wind implantation. Small amounts of these materials can be provided to investigators who would find them useful.

Minkin, J. A.↗

Sources of Li isotope bias during SIMS analysis of standard glasses

The 7 Li/ 6 Li ratios in fourteen USGS, MPI-DING, and NIST glass reference materials (RMs) were analyzed by LG-SIMS to assess compositional matrix effects, evaluate RM δ 7 Li homogeneity, and calculate the useful yield of lithium in silicate glasses. The analyzed RMs cover a range of SiO 2 contents from 45.5 to 75.6% (komatiite to rhyolite), the largest compositional range yet evaluated for δ 7 Li matrix effects. We observe a matrix-induced bias (matrix effect) of up to 18‰ over the studied range that linearly correlates with SiO 2 content, demonstrating that SiO 2 content is a critical factor that must be considered when using silicate glasses to standardize for silicate samples of unknown δ 7 Li composition. All RMs were found to be sufficiently reproducible to aid in standardization of variable SiO 2 contents and appear isotopically homogeneous at the precision of our measurements. Lithium ionizes very efficiently in these RMs, with measurable yields >5% in all fused-rock RMs and >15% in low SiO 2 fused-rock RMs measured at high beam intensities. Finally, fused-rock RMs ionize lithium 2-3x more efficiently than synthetic glass RMs, which may be related to differences in major oxide chemistry and the reduced nature of the synthetic glasses relative to their fused counterparts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗