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At least 307 records · Page 17
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Exploring the Jezero Delta Front: Overview of Results From the Mars 2020 Perseverance Rover’s Second Science Campaign

The Perseverance rover landed in Jezero crater on February 18, 2021, with the mission goals to explore the geology, astrobiological potential, and modern environment of the crater floor and delta, and to collect and cache well-documented samples for Mars Sample Return. After completion of the “Crater Floor” science campaign, the rover conducted a rapid traverse (sols 379-414) to the Three Forks region of the crater floor adjacent to the delta front. From here, Perseverance’s second “Delta Front” science campaign (DFC) began on Sol 415, April 20, 2022. The DFC has explored two lobes of the delta front, the neighboring crater floor, and their contact zone, focusing on the lowest geologic exposures composing the Jezero delta (largely mapped within the delta “thin layered unit”). As of January 1, 2023, Perseverance has covered 14325 km of traverse distance and collected 15 rock sample cores, 2 regolith samples, 1 atmospheric sample, and 3 witness tubes, employing a sample pair strategy where each unique sample is paired with a companion sample core from the same location, to enable the construction of two different caches. After sample depot construction at Three Forks, the DFC will conclude upon re-ascent of the delta front, and the next “Delta Top” science campaign will start.

Mars 2020 Mission↗
NASA NTRS1988

Early Precambrian crustal evolution in Eastern India: The ages of the Singhbhum granite and included remnants of older gneiss

Geochronology of samples from the Indian Shield was discussed. New Sm-Nd data was given for the Singhbhum granite, which give model ages (T sub DM of 3.36 to 3.40 Ga, essentially equivalent to ages of included gneissic remnants of the older metamorphic group (OMG) (T sub DM = 3.35 to 3.41 Ga). Lead-lead and Rb-Sr ages of the granite and OMG range between 3.28 to 3.38 Ga. These results are considerably younger than the 3775 + or - 89 Ma Sm-Nd isochron of Basu et al., which Taylor and colleagues interpret as an artifact caused by regressing two suites of unrelated rock samples.

Moorbath, Stephen↗
DOE OSTI2020

Foot-scale Evaluation of CO2-Responsive Polymer and CO2 Binary Fluid as an Alternative Fracturing Fluid for Enhanced Geothermal Systems

A foot-scale high-temperature true-triaxial fracturing apparatus was used to conduct hydraulic fracture tests on rock samples. The fracturing tests used different fluids including water, CO2, CO2 with water, and CO2 with a 1% polyallylamine (PAA)/water solution. The tests were conducted with both constant pressure injection and constant flow rate injection modes. CO2-based fracturing fluids were found to produce higher breakdown pressures, high transient flow rates, and produce higher-conductivity fractures as compared to water-based fracturing fluids. Additionally, faster pressurization rates with CO2-based fracturing fluids (obtained when fracturing at constant flow rate mode) are found to be associated with higher fracture conductivities. When fracturing with CO2-based fluids in the presence of a PAA aqueous solution, for example if the rock is saturated with 1wt% PAA in water, the volume expansion caused by CO2-induced crosslinking of PAA leads to a faster pressure increase due to the associated volume expansion and increase in viscosity. It was also found that CO2 as a fracturing fluid injected in hot dry rock (HDR) attain the highest fracture conductivity only when injected at very high flow rates, followed very closely by the CO2/PAA fracturing fluid system that generates fractures with, on average, similarly high conductivity values though independently of injection flow rate and using 1/6 of the mass of CO2 as compared to CO2 in HDR. Breakdown pressures were also similar for CO2 stimulation in HDR and CO2/PAA fluid system under identical injection flow rates. Finally, the well-known low viscosity of CO2 phase prevents the efficient transport of proppants while the reacted CO2/PAA fluid system is known to form a high viscosity binary fracturing fluid system with the potential to carry proppant in addition of being a fine fracturing fluid.

Enhanced Geothermal Systems, polyallylamine, Co2-r↗
DOE OSTI2017

Simplified Pore Network Model for Analysis of Flow Capacity and Residual Oil Saturation Distribution Based on Computerized Tomography

The pore network (connected tunnels) can be used not only to describe pore geometry inside a rock but also to calculate various fluid flow properties on a micro scale. Based on a “digital core” extracted from micro computerized tomography (μ-CT), we have developed a simplified pore network model. This study simplifies the pore structure as a lattice of cubes. Pore size, pore distribution, tunnel connectivity, fluid viscosity, interfacial tension, and the external driving pressure gradient are considered for each adjacent cube to evaluate the flow capacity of the pore network. We calculated the permeability, effective permeability, and effective sweep efficiency. The results show that fluid flow initially starts in the largest tunnel, which corresponds to the threshold pressure of the rock sample (fluid flow onset pressure). Permeability changes nonlinearly before all the tunnels are involved in the flow. Changes in the microscopic residual oil saturation and the sweep efficiency were visualized based on the three-dimensional pore distribution. Visualization shows that more oil remains in the formation, the heterogeneity is greater, and the oil viscosity is higher.

58 GEOSCIENCES↗
NASA NTRS1997

Constraints on the Nature and Distribution of Iridium Host Phases at the Cretaceous-Tertiary Boundary: Implications for Projectile Identity and dispersal on impact

Among Cretaceous-Tertiary boundary sites worldwide, variations in the concentrations and ratios of elements commonly enriched in meteorites complicate traditional geochemical attempts at impactor identification. Yet they may provide constraints on the physical and chemical processes associated with large-body disruption and dispersal, as well as with diagenesis of projectile components. To this end, we continue our efforts to identify the mineral host-phases of projectile-derived elements, particularly for Ir, and to document their partitioning between crater deposits and ejecta resulting from the Chicxulub basin-forming impact. Building on earlier work, we used INAA to measure Ir concentrations in successively smaller splits of finely powdered impact melt breccia from the Chicxulub Crater in Mexico (sample Y6Nl9-R(b)), and K/T boundary fish clay from Stevns Klint, Denmark (sample FC-1, split from 40 kg of homogenized material intended as an analytical standard). Results for the Chicxulub sample show a heterogeneous Ir distribution and document that at least five discrete Ir-bearing host phases were isolated in subsequent splits, having Ir masses equivalent to pure Ir spheres from about 0.8 to about 3.5 mm in diameter. Three of these are within a sufficiently reduced mass of powder to warrant searching for them using backscattered electron microscopy. In contrast, successively smaller splits of the Stevns Klint fish clay show no statistically significant deviation from the reported value of 32 +/- 2 ng/g Ir, suggesting a uniform Ir host-phase distribution. For the smallest split obtained thus far (100 +/- 40 ng/g Ir), a pure Ir sphere of equivalent Ir mass would be <0.05 min in diameter. (n.b. Although homogenizing and sieving of FC-1 to <75 min obviously obscured variations in stratigraphic distribution, it is unlikely to have affected the size-frequency distribution of Ir host phases.) We previously identified micrometer-scale Ir host phases by electron microscopy in melt-rock samples from two widely separated drill holes at the Chicxulub Basin, including a replicate split of Y6-NI9-R. One is an aggregate of subhedral Ir metal grains enclosed in silicate, in which no other Pt group elements (PGE) were detected. A second particle with twice the mass as the first, concentrated predominantly in a single grain, is associated with minor concentrations of Os, Ru, and Pt, and with adhering particles of corundum and perovskite. A third Ir-rich particle, with a greater apparent Os concentration, was identified before being lost as a result of charging under the electron beam. In addition to demonstrating the preservation of projectile components within the Chicxulub Crater, analogous phase associations in Ca- and Al-rich inclusions (CAI) from C2 and C3 chondrites suggest to us that these melt-rock Ir host phases are relics from a carbonaceous chondrite K/T boundary impactor Although the obviously low Ru/Ir ratios of the Chicxulub Ir host phases are qualitatively consistent with suggested PGE fractionation with distance during condensation in an ejecta cloud, it seems difficult to explain the accumulation of the about 3 x 10(exp 11) Ir atoms required to form a about 10(exp -10) g nugget of pure Ir metal within a jet of vaporized projectile expanding at 1-4 km/s, or to effectively exclude or remove commonly alloyed PGE and siderophile elements by fractionation processes resulting from condensation, oxidation, sulfidization, exsolution, or autometamorphism during cooling of the melt. We do not dismiss the importance of these processes entirely; on the contrary, other geochemical and mineralogical aspects of the melt rocks require them, and condensation from the expanding ejecta cloud appears to best explain the primary Ir host-phase distribution in the fish clay, as well as the high Ir concentrations associated with spinel-bearing spheroids at the K/T boundary in the Pacific Ocean . If the "relict" hypothesis is correct, micronuggets of other PGEs and alloys, not detected by our INAA screening, should also occur in the melt rocks. Possibly, the discrete host phases with lesser Ir masses are such alloys with subordinate Ir, rather than simply smaller, predominantly Ir-bearing particles. A CAI source for the relics would be consistent with either a comet or an asteroid K/T impact at Chicxulub. (Additional information contained in the original.)

Schuraytz, B. C.↗
DOE OSTI2017

Effective Pressure Law for the Intrinsic Formation Factor in Low Permeability Sandstones: EPL law for the formation factor

The effective pressure law for the intrinsic formation factor of low permeability sandstones from the Ordos Basin (northwest of China) was studied experimentally by measuring the electrical resistivity of brine saturated rock samples while cycling the pore and confining pressures, p p and p c . We used a 100,000 ppm NaCl solution so that the results could be directly interpreted in terms of the intrinsic formation factor F. The Response Surface method was used to construct a quadratic function of pp and pc fitting the experimental data, from which the coefficient α of the effective pressure law, p eff = p c – αp p , was determined. We found that the coefficient α generally had low values, mainly from 0.2 to 0.4, thus contradicting the theoretical prediction that α should be equal to 1 for scale-invariant properties, such as F, in linear elastic materials having a homogeneous solid matrix. Since the two underlying assumptions, linear elasticity and homogeneity of the solid matrix, are likely violated in reservoir rocks, we tried to assess their effects on α using simple analytical models, based on idealized geometries of the pore and solid phases. Analysis of these models suggests that non-linear elasticity associated with the formation of solid–solid contacts in the compressed rocks (e.g., during closure of rough cracks or crack-like pores along the grain boundaries), may be more effective in producing the low α values observed than inhomogeneity of the solid matrix.

58 GEOSCIENCES↗
NASA NTRS1993

Mars rover sample return mission utilizing in situ production of the return propellants

This paper presents an unmanned Mars sample return mission that utilizes propellants manufactured in situ from the Martian atmosphere for the return trip. A key goal of the mission is to demonstrate the considerable benefits that can be realized through the use of indigenous resources and to test the viability of this approach as a precursor to manned missions to Mars. Two in situ propellant combinations, methane/oxygen and carbon monoxide/oxygen, are compared to imported terrestrial hydrogen/oxygen within a single mission architecture, using a single Earth launch vehicle. The mission is assumed to be launched from Earth in 2003. Upon reaching Mars, the landing vehicle aerobrakes, deploys a small satellite, and lands on the Martian surface. Once on the ground, the propellant production unit is activated, and the product gases are liquefied and stored in the empty tanks of the Earth Return Vehicle (ERV). Power for these activities is provided by a dynamic isotope power system. A semiautonomous rover, powered by the indigenous propellants, gathers between 25 and 30 kg of soil and rock samples which are loaded aboard the ERV for return to Earth. After a surface stay time of approximately 1.5 years, the ERV leaves Mars for the return voyage to Earth. When the vehicle reaches the vicinity of Earth, the sample return capsule detaches, and is captured and circularized in LEO via aerobraking maneuvers.

Bruckner, A. P.↗
DOE OSTI2015

Nuclear forensics: Soil content

Nuclear Forensics is a growing field that is concerned with all stages of the process of creating and detonating a nuclear weapon. The main goal is to prevent nuclear attack by locating and securing nuclear material before it can be used in an aggressive manner. This stage of the process is mostly paperwork; laws, regulations, treaties, and declarations made by individual countries or by the UN Security Council. There is some preliminary leg work done in the form of field testing detection equipment and tracking down orphan materials; however, none of these have yielded any spectacular or useful results. In the event of a nuclear attack, the first step is to analyze the post detonation debris to aid in the identification of the responsible party. This aspect of the nuclear forensics process, while reactive in nature, is more scientific. A rock sample taken from the detonation site can be dissolved into liquid form and analyzed to determine its chemical composition. The chemical analysis of spent nuclear material can provide valuable information if properly processed and analyzed. In order to accurately evaluate the results, scientists require information on the natural occurring elements in the detonation zone. From this information, scientists can determine what percentage of the element originated in the bomb itself rather than the environment. To this end, element concentrations in soils from sixty-nine different cities are given, along with activity concentrations for uranium, thorium, potassium, and radium in various building materials. These data are used in the analysis program Python.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2012

In Situ Geochemical Analysis and Age Dating of Rocks Using Laser Ablation-Miniature Mass Spectrometer

A miniaturized instrument for performing chemical and isotopic analysis of rocks has been developed. The rock sample is ablated by a laser and the neutral species produced are analyzed using the JPL-invented miniature mass spectrometer. The direct sampling of neutral ablated material and the simultaneous measurement of all the elemental and isotopic species are the novelties of this method. In this laser ablation-miniature mass spectrometer (LA-MMS) method, the ablated neutral atoms are led into the electron impact ionization source of the MMS, where they are ionized by a 70-eV electron beam. This results in a secondary ion pulse typically 10-100 microsecond wide, compared to the original 5-10-nanosecond laser pulse duration. Ions of different masses are then spatially dispersed along the focal plane of the magnetic sector of the miniature mass spectrometer and measured in parallel by a modified CCD (charge-coupled device) array detector capable of detecting ions directly. Compared to conventional scanning techniques, simultaneous measurement of the ion pulse along the focal plane effectively offers a 100% duty cycle over a wide mass range. LAMMS offers a more quantitative assessment of elemental composition than techniques that detect laser-ionized species produced directly in the ablation process because the latter can be strongly influenced by matrix effects that vary with the structure and geometry of the surface, the laser beam, and the ionization energies of the elements. The measurement of high-precision isotopic ratios and elemental composition of different rock minerals by LAMMS method has been demonstrated. The LA-MMS can be applied for the absolute age determination of rocks. There is no such instrument available presently in a miniaturized version that can be used for NASA space missions. Work is in progress in the laboratory for geochronology of rocks using LA-MMS that is based on K-Ar radiogenic dating technique.

Sinha, Mahadeva P.↗
NASA NTRS2018

Field Camp for Astronauts: NASA's Geoscience Training Program for Planetary Exploration

Fifty years ago Apollo astronauts walked on the Moon to explore the geology and collect samples for Earth return. Several authors have discussed the strategic planning and training that enabled the Apollo successes, and assembled recommendations regarding today’s lunar science objectives and astronaut training required to achieve those science goals. Since the 1980s, geoscience training for astronauts focused on observing the Earth from orbit. Today, we are building a geoscience training program to support informed Earth observations as well as the exploration culture for future human missions to the Moon and Mars. Our team partnered with JSC’s crew training and astronaut offices to develop our 4-week geoscience program for the 2017 astronaut class. Because the astronauts have a variety of professional backgrounds, we provide a broad introduction to Earth and planetary sciences. But our prime focus is 2 weeks of intensive field work, a methodology introduced with the 2013 astronaut class. We completed the first half of the training – a field trip to observe hurricane deposits along Galveston Bay; keynotes by Apollo colleagues highlighting Apollo experiences; a tightly-integrated week of introductory geology in the classroom followed by a week of fieldwork in the Rio Grande del Norte National Monument. The classroom included interactive map exercises that allowed the students to progressively build a base map of the field area that they used as a starting point for their week-long mapping exercise. We divided the class into small mapping groups to conduct their observations, mapping and interpretation of the geology. In addition to learning geological field work, our field training provided the platform for practicing expeditionary leadership, a key skill set valued by NASA for astronaut crews. Next summer the capstone fieldwork for the 2017 astronauts will include both mapping and rock sampling. Throughout the mapping, the class will collect additional data to help inform field and sampling decisions using diagnostic field instruments that are being tested in analog settings for their operational efficacy for future planetary exploration.

Evans, Cynthia A.↗
DOE OSTI2022

Deep-learning-based workflow for boundary and small target segmentation in digital rock images using UNet++ and IK-EBM

We report three-dimensional (3D) X-ray micro-computed tomography (μCT) has been widely used in petroleum engineering because it can provide detailed pore structural information for a reservoir rock, which can be imported into a pore-scale numerical model to simulate the transport and distribution of multiple fluids in the pore space. The partial volume blurring (PVB) problem is a major challenge in segmenting raw μCT images of rock samples, which impacts boundaries and small targets near the resolution limit. We developed a deep-learning (DL)-based workflow for accurate and fast partial volume segmentation. The DL model's performance depends primarily on the training data quality and model architecture. This study employed the entropy-based-masking indicator kriging (IK-EBM) to segment 3D Berea sandstone images as training datasets. The comparison between IK-EBM and manual segmentation using a 3D synthetic sphere pack, which had a known ground truth, showed that IK-EBM had higher accuracy on partial volume segmentation. We then trained and tested the UNet++ model, a state-of-the-art supervised encoder-decoder model, for binary (i.e., void and solid) and four-class segmentation. We compared the UNet++ with the commonly used U-Net and wide U-Net models and showed that the UNet++ had the best performance in terms of pixel-wise and physics-based evaluation metrics. Specifically, boundary-scaled accuracy demonstrated that the UNet++ architecture outperformed the regular U-Net architecture in the segmentation of pixels near boundaries and small targets, which were subjected to the PVB effect. Feature map visualization illustrated that the UNet++ bridged the semantic gaps between the feature maps extracted at different depths of the network, thereby enabling faster convergence and more accurate extraction of fine-scale features. The developed workflow significantly enhances the performance of supervised encoder-decoder models in partial volume segmentation, which has extensive applications in fundamental studies of subsurface energy, water, and environmental systems.

02 PETROLEUM↗
DOE OSTI2014

Pore-scale intermittent velocity structure underpinning anomalous transport through 3-D porous media

We study the nature of non-Fickian particle transport in 3-D porous media by simulating fluid flow in the intricate pore space of real rock. We solve the full Navier-Stokes equations at the same resolution as the 3-D micro-CT (computed tomography) image of the rock sample and simulate particle transport along the streamlines of the velocity field. We find that transport at the pore scale is markedly anomalous: longitudinal spreading is superdiffusive, while transverse spreading is subdiffusive. We demonstrate that this anomalous behavior originates from the intermittent structure of the velocity field at the pore scale, which in turn emanates from the interplay between velocity heterogeneity and velocity correlation. Finally, we propose a continuous time random walk model that honors this intermittent structure at the pore scale and captures the anomalous 3-D transport behavior at the macroscale.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Wettability measurement under high P-T conditions using X-ray imaging with application to the brine-supercritical CO 2 system

We present a new method for measuring wettability or contact angle of minerals at reservoir pressure-temperature conditions using high-resolution X-ray computed tomography (HRXCT) and radiography. In this method, a capillary or a narrow slot is constructed from a mineral or a rock sample of interest wherein two fluids are allowed to form an interface that is imaged using X-rays. After some validation measurements at room pressure-temperature conditions, we illustrate this method by measuring the contact angle of CO 2 -brine on quartz, muscovite, shale, borosilicate glass, polytetrafluoroethylene (PTFE or Teflon), and polyether ether ketone (PEEK) surfaces at 60–71°C and 13.8–22.8 MPa. At reservoir conditions, PTFE and PEEK surfaces were found to be CO 2 -wet with contact angles of 140° and 127°, respectively. Quartz and muscovite were found to be water-wet with contact angles of 26° and 58°, respectively, under similar conditions. Borosilicate glass-air-brine at room conditions showed strong water-wet characteristics with a contact angle of 9°, whereas borosilicate glass-CO 2 -brine at 13.8 MPa and 60°C showed a decrease in its water-wetness with contact angle of 54°. This method provides a new application for X-ray imaging and an alternative to other methods.

58 GEOSCIENCES↗
DOE OSTI2017

Numerical investigation of Lower Tuscaloosa Sandstone and Selma Chalk caprock under geological CO 2 sequestration conditions: mineral precipitation and permeability evolution

Abstract A numerical model was developed using CrunchFlow to simulate reactive transport and porosity and permeability changes of sandstone and carbonate rock samples taken from the Lower Tuscaloosa Formation and the Selma Chalk Formation, Jackson County, MS, USA. The model predicted a permeability decrease from 2190 mD to 2038 mD for the Lower Tuscaloosa Sandstone sample in a static batch reactor after 180 days of exposure to CO 2 ‐saturated brine, which is consistent with measured permeability results. The model predicted a negligible permeability change from 2.00 mD to 2.08 mD for the Selma Chalk carbonate sample after 180 days of exposure to CO 2 ‐saturated brine. Based on model prediction, key mineral dissolution and precipitation reactions in the Lower Tuscaloosa Sandstone sample include dissolution of quartz, chlorite, and feldspar, as well as precipitation of amorphous silica and kaolinite. For the Selma Chalk carbonate sample, key predicted reactions include dissolution of calcite, quartz and chlorite, and precipitation of kaolinite and amorphous silica. Initial porosity, initial feldspar content and the exponent n value (related to pore structure and tortuosity) used in permeability calculations were three important factors affecting permeability evolution of sandstone samples under CO 2 sequestration conditions. The small permeability change predicted for both the Lower Tuscaloosa Sandstone and the Selma Chalk caprock after exposure to CO 2 ‐saturated brine suggests that poro‐permeability changes during CO 2 injection into the Lower Tuscaloosa Formation are not likely to significantly affect reservoir and seal quality. © 2017 Society of Chemical Industry and John Wiley & Sons, Ltd.

Zhang, Liwei↗
DOE OSTI2019

Rare earth elements and radiogenic strontium isotopes in carbonate minerals reveal diagenetic influence in shales and limestones in the Appalachian Basin

Rare earth element (REE) signatures are often applied to interpret paleoenvironmental conditions in sedimentary basins, however the complicated diagenetic histories in dynamic depositional environments can affect interpretation of measured REE signatures. Prior studies on REE content in shales and limestones indicated that REE in specific mineral phases may provide unique information concerning diagenetic reactions occurring in sedimentary rocks during burial and compaction. Application of sequential extraction techniques to target REE signatures in specific mineral fractions may provide greater insight into the complex processes that occurred during diagenesis and catagenesis. Thus, using this technique, this study provides a detailed account for REE, 87 Sr/ 86 Sr, and δ 13 C in the carbonate fraction of the Marcellus Shale and adjacent formations in the Appalachian Basin. A suite of 49 rock samples collected from two cores recovered from Monongalia County, West Virginia, USA was analyzed. The results showed that the carbonate concretions in calcareous shales and carbonate cements in black shales were very distinct. The REE plus yttrium (REY) were more concentrated in the carbonate concretions than in the carbonate cements. The carbonate concretions displayed REY patterns that are closely similar to modern seawater, while MREE-enrichment was observed in the carbonate cements. Likewise, the 87 Sr/ 86 Sr values in the carbonate concretions were similar to those measured for unaltered Middle Devonian carbonates, while the 87 Sr/ 86 Sr in the carbonate cements were much more radiogenic. This observation indicates that the carbonate cement could have been inherited radiogenic 87 Sr expulsed from clays during illite-smectite transition. Overall, this study demonstrated two distinct processes involved with controlling the carbonate geochemistry within Appalachian Basin shales and limestones: one fraction displaying minimal diagenetic alteration relative to depositional conditions (carbonate concretions in calcareous shales and limestone carbonate in limestones), and another fraction displaying the evidence for extensive chemical alteration during illite-smectite transition and catagenesis (carbonate cements in black shales). Here, in addition, highly variable and significant enrichments of U and Mo demonstrate that the Union Spring member and the Lower Oatka Creek member of the Marcellus Shale in the southwestern Appalachian Basin (MSEEL site) were deposited under mainly anoxic environment whereas intermitted episodes of dysoxic to perhaps oxic conditions occurred during the deposition of the Upper Oatka Creek member.

58 GEOSCIENCES↗
DOE OSTI2023

Distribution of rare earth and other critical elements in lignites from the Eocene Jackson Group, Texas

Coal is increasingly evaluated as a source of rare earth elements (REEs) in the United States to address the overreliance on imported REEs. The objective of this study was to assess the distribution of REEs in lignites from selected mining areas in the Texas Gulf Coastal Plain region. Thirty-one archived lignite and rock samples previously collected by the U.S. Geological Survey were analyzed for their rare earth element and critical mineral content. These include samples from one core (5400 and 5500 lignite horizons) and two opencast lignite mines (Gibbons Creek 3500 and 4500 horizons, and San Miguel horizons A to D) in the Eocene Jackson Group of the Texas Gulf of Mexico Coastal Plain. Some lithologies in the Gibbons Creek 3500 and 4500 lignite-bearing sections have high total rare earth, yttrium (Y), and scandium (Sc) (REYSc) values, up to 7800 ppm (ash basis) REYSc. The lignite lithologies show an enrichment in rare earths, [samarium (Sm) through gadolinium (Gd)]. The basal Gibbons Creek 3500 lignite bench shows a heavy rare earth element enrichment pattern resembling that often seen in peats through high volatile A bituminous coals. The 5500 lignite sequence, overlying the latter lignite sections, shows a light rare earth enrichment. The San Miguel lignite benches have heavy rare earth enrichments with a negative europium (Eu) anomaly.

58 GEOSCIENCES↗
DOE OSTI2021

Distribution of rare earth elements and other critical elements in beneficiated Pennsylvania anthracites

The Pennsylvania Anthracite Fields are in a complex tectonic and metamorphic terrain, historically hosting one of the largest concentrations of coal mining in the USA. Anthracite mining now largely consists of the surface mining of the pillars remaining from the prime years of underground mining. The geochemical study of the sized coal products and the refuse (largely rock) from three preparation plants (breakers) demonstrates that Principal components analysis (PCA) of select major oxide, minor element, and rare earth elements illustrates some differentiation among the products from the individual plants. The rock samples, with abundant quartz and metamorphic Al-Si minerals and with a lower ash-basis REE concentration than the coals, were distinctly separated from the coal samples on the PCA plots. Plots of Gd N /Gd N * vs. Eu N /Eu N * and Ce N /Ce N * vs. Eu N / Eu N * showed differentiation between the individual suites of coals showed that the refuse samples had distinct REE distributions compared to the associated coals. Further, several minor and trace elements show enrichments in the coal samples. Lithium, with concentrations of up to 314 ppm on an ash basis, is among the most promising of the critical elements, exceeding the enrichment of the REY and Sc.

58 GEOSCIENCES↗
DOE OSTI2020

Sulfur isotope fractionation between aqueous and carbonate-associated sulfate in abiotic calcite and aragonite

Sulfate (SO 4 2– ) incorporated into calcium carbonate minerals enables measurements of sulfur (S) isotope ratios in carbonate rocks. This Carbonate Associated Sulfate (CAS) in marine carbonate minerals is thought to faithfully represent the S isotope composition of the seawater sulfate incorporated into the mineral, with little or no S isotope fractionation in the process. However, comparison between different calcifying species reveals both positive and negative S isotope fractionation between CAS and seawater sulfate, and a large range of S isotope ratios can be found within a single rock sample, depending on the component measured. To better understand the isotopic effects associated with sulfate incorporation into carbonate minerals, we precipitated inorganic calcite and aragonite over a range covering more than two orders of magnitude of sulfate concentration and precipitation rate. Coupled measurements of CAS concentration, S isotope composition and X-ray absorption near-edge spectra (XANES) permit characterization and explanation of the observed dependence of S isotope fractionation between CAS and aqueous sulfate (CAS-SO 4 2– isotope fractionation) on sulfate concentration and precipitation rate. In aragonite, the CAS-SO 4 2– isotope fractionation is 1.0 ± 0.3‰ and independent of the sulfate (and CAS) concentration. In contrast, we note the CAS-SO 4 2– isotope fractionation in calcite covaries strongly with the sulfate concentration and weakly with the precipitation rate, between values of 1.3 ± 0.1 and 3.1 ± 0.6‰. We suggest that the correlation between aqueous sulfate concentration and CAS-SO 4 2– isotope fractionation in calcite reflects a dependence of the equilibrium S isotope fractionation on the concentration of CAS, through the effect of the sulfate impurity on the carbonate mineral’s energetic state.

58 GEOSCIENCES↗