Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “geoscience”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 973 records · Page 54
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Hydrothermal solubility of Dy hydroxide as a function of pH and stability of Dy hydroxyl aqueous complexes from 25 to 250 °C

The rare earth elements (REE) have important applications in green energy technologies. The formation of mineral deposits in geologic systems commonly involves hydrothermal fluids which can mobilize the REE. However, the REE speciation is not well known as a function of pH. The thermodynamic properties of REE hydroxyl complexes used in geochemical models are based on the Helgeson-Kirkham-Flowers (HKF) equation of state parameters which were derived by extrapolation of low temperature experimental and estimated data. In this study, Dy hydroxide solubility experiments are combined with available literature data to improve these models from 25 to 250 °C and optimize the thermodynamic properties of Dy 3+ and Dy hydroxyl complexes using GEMSFITS. Batch-type solubility experiments were conducted from 150 to 250 °C and at saturated water vapor pressure in perchloric acid solutions with initial pH values of 2 to 5 in 0.5 pH unit increments. The measured solubility of Dy hydroxide is retrograde with temperature and decreases with pH. The logarithm of total dissolved Dy molality ranges from –2.3 to –5.3 at 150 °C (pH 4.7–5.5), from –2.4 to –5.6 at 200 °C (pH 3.9–5.1), and from –3.7 to –6.9 at 250 °C (pH of 3.4 and 5.0). The optimized standard partial molal Gibbs energies of formation (Δ f G° T ) derived for Dy 3+ and DyOH 2+ display a close to linear relationship with temperature, fitting with previous optimizations based on DyPO 4 solubility data in the literature. A comparison of the optimized ΔfG°T values for aqueous Dy species with predictions from available HKF parameters indicates significant differences ranging from +11 to –26 kJ/mol between 25 and 250 °C. The experimental fits are used to derive the Dy hydroxide solubility products (K s0 ) and formation constants for the hydrolysis of Dy (β n with n = 1 to 3; Dy 3+ + nOH – = DyOH n 3-n ) as a function of temperature. The optimization method presented yields accurate thermodynamic properties for the Dy 3+ aqua ions and the DyOH 2+ species at the acidic to mildly acidic pH studied whereas more experimental work is needed at near-neutral and alkaline conditions to better constrain the other hydroxyl complexes. Furthermore, the optimized thermodynamic data have a significant impact on geochemical modeling of the mobility and solubility of REE minerals in acidic hydrothermal fluids.

58 GEOSCIENCES↗
DOE OSTI2025

Interaction between dissolution and precipitation during olivine carbonation: Implications for CO 2 mineralization

Large-scale carbonation of olivine is considered a promising approach for in situ mineral carbonation, offering a permanent and stable method for CO 2 storage. A critical aspect of this process is understanding how dissolution and precipitation interact, as this could drive fracturing and enhance further reactions. In this study, we conducted carbonation experiments on olivine using CO 2 -saturated aqueous solutions of NaHCO 3 and NaCl. Two experimental setups were used: one representing an open geochemical system and the other a closed system, corresponding to reaction-limited and flow-limited scenarios, respectively. Further, post-reaction textural analysis using scanning electron microscopy (SEM) revealed surface coatings of reaction products in the closed system, while etch pits and etch channels were prevalent in the open system. Although no direct evidence of reaction-driven fracturing was observed, etch pits and etch channels may serve as initiation points for subcritical crack formation and growth, potentially maintaining permeability and exposing new unreacted surfaces. Using linear elastic fracture mechanics (LEFM) model, we estimate that microcracks could propagate under a pressure of 0.1 GPa if reaction products accumulate within the etch pits. Our findings offer new insights into the mechanisms governing olivine carbonation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Quantification of the REE 3+ aqua ions and chloride species in aqueous fluids by in situ Raman spectroscopy using perturbations of the water band

Acidic NaCl-rich aqueous fluids play a crucial role in forming hydrothermal rare earth elements (REE) mineral deposits. Aqueous REE mobility is mostly controlled by the stabilities of REE 3+ and REE chloride species. Our current knowledge of REE speciation is based on solubility data, thermodynamic models and in situ spectroscopic measurements, sometimes coupled with molecular simulations. Here, in this study, we investigate Nd and Yb speciation in pH2 Cl-bearing solutions at 25 °C and 0.1 MPa with variable Cl/REE ratios using Raman Spectroscopy in solutions with 0.1 to 0.6 mol/kg NdCl 3 or YbCl 3 and 0.2 to 3.2 mol/kg NaCl. Due to the challenges in resolving the REE-Cl band, we developed a new method using the water vibrational mode and multivariate curve resolution (MCR) analysis. The Raman spectra for the vibrational band of water (2700 to 3900 cm –1 ) were collected at 25 °C and fitted by three Gaussian sub-peaks, then quantified using MCR analysis to de-convolute the water band into bulk H 2 O and the perturbations caused by of Cl – , REE 3+ , and REE chloride species. REE speciation based on the perturbations of the water band indicates that REE 3+ aqua ions dominate acidic solutions at 25 °C, but up to ~20 mol% YbCl 2+ forms at high YbCl 3 concentrations. The new method is promising for quantifying in situ speciation of the REE 3+ aqua ions and REE chloride species in aqueous fluids while providing information on the hydration of ions. This method improves our molecular level understanding of REE aqueous species stability and their role in REE mobilization during fluid-rock interaction.

58 GEOSCIENCES↗
DOE OSTI2025

Spectrophotometric determination of the stability of La hydroxyl complexes at near neutral to alkaline pH from 25 to 75 °C

The hydrolysis of rare earth elements (REE) potentially controls their mobility during fluid-rock interaction in a broad range of pH and temperature conditions. However, there is still a lack of thermodynamic data for modeling accurately the stability of REE hydroxyl complexes in hydrothermal aqueous fluids. Here, in this study, UV–Vis spectrophotometric experiments were conducted from 25 to 75 °C in near-neutral to alkaline NaOH-bearing aqueous solutions with varying lanthanum (La) concentrations (0 to ∼0.23 mmol/kg). The color indicator m-cresol purple was used to determine in situ pH and derive the average OH− ligand number ($\overrightarrow{n}$) and formation constants for the La hydroxyl complexes (LaOH 2+ , La(OH) 2 + , and La(OH) 3 0 ). From 25 to 50 °C, $\overrightarrow{n}$ ranges between ∼1 and 2 at pH from 7.0 to 9.3. At 75 °C, $\overrightarrow{n}$ ranges between ∼1.5 and 3 at pH from 6.3 to 8.8. These results suggest the predominance of LaOH 2+ and La(OH) 2 + complexes from 25 to 50 °C, and an increased predominance of La(OH) 3 0 at 75 °C. The cumulative formation constants (β n °, n = 1 to 3) are derived for the reaction La 3+ + nOH − = La(OH) n 3-n , and fitted between 25 and 250 °C by combining the UV–Vis and literature solubility data. The resulting logβ n ° are expressed as function of temperature (T in Kelvin): logβ 1 ° = −1.786 + 0.0133 T + 1.049·10 3 /T; logβ 2 ° = −5.797 + 0.0267 T + 2.713·10 3 /T; logβ 3 ° = 6.435 + 0.0223 T + 512.7/T. A comparison between these new fits and existing extrapolations using the Helgeson-Kirkham-Flowers equation of state indicates significant differences in the predicted hydrolysis of La. The latter extrapolations should therefore be updated for the hydrolysis of REE.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Selective transport of light vs. heavy rare earth elements by sulfate/bisulfate complexes in hydrothermal fluids

Here, this study explores the transport of rare earth elements (REE) in acidic sulfate-bearing hydrothermal fluids and the implications for the fractionation of light/heavy REE in critical mineral deposits. The speciation of Nd (light REE) and Yb (heavy REE) sulfate complexes were determined via in situ Raman spectroscopy using fused SiO 2 capillary cells up to 300 ºC at saturated water vapor pressure and in a hydrothermal diamond anvil cell up to 500 ºC and 540 MPa. The REE monosulfate (REESO 4 + ) and REE disulfate (REE(SO 4 ) 2 - ) species are stable below 150 to 250 ºC but become less stable at higher temperatures, particularly the light REE, due to the decreased solubility of REE sulfate solids. At higher pressure, these REE sulfate complexes display an increased stability field up to 400 ℃. The REE bisulfate complex (REEHSO 4 2+ ) was identified with a wide stability field below 400 ºC for the HREE in acidic Yb 2 (SO 4 ) 3 -bearing solutions, whereas in Nd 2 (SO 4 ) 3 -bearing solutions, the LREE bisulfate complex is restricted to below 100 ℃. These results suggest that bisulfate is a previously unrecognized selective ligand for heavy REE transport at low temperature in acidic oxidized hydrothermal fluids. Such fluids are responsible for hydrothermal alteration in many REE deposits. Prediction of phase stabilities across pressure, temperature, and composition space (P-T- x ) is crucial for predicting the role of aqueous REE sulfate complexes in the mobilization of REE in crustal fluids.

58 GEOSCIENCES↗
DOE OSTI2020

Origin of tungsten and geochemical controls on its occurrence and mobilization in shallow sediments from Fallon, Nevada, USA

In this study, tungsten (W) occurrence and speciation was investigated in sediments collected from Fallon, Nevada where previous studies have linked elevated W levels in human body fluids to an unusual cluster of childhood leukemia cases. The speciation of sedimentary W was determined by μ-XRF mapping and μ-XANES. The W content of the analyzed surface sediments ranged between 81 and 25,908 mg/kg, which is significantly higher than the W content in deeper sediments which ranged from 37 to 373 mg/kg at 30 cm depth. The μ-XANES findings reveal that approximately 20–50% of the total W in the shallow sediment occurs in the metallic form (W 0 ); the rest occurs in the oxide form (W VI O 3 ). Because W 0 does not occur naturally, its elevated concentrations in surface sediments point toward a possible local anthropogenic origin. The oxidation of metallic W 0 with meteoric waters likely leads to the formation of W VI O 3 . The chief water-soluble W species was identified as WO 4 2– by chromatographic separation and speciation modeling. These results led us to postulate that W 0 particles from a currently unknown but local source(s) is (are) deposited onto the soils and/or surface sediments. The W 0 in interaction with meteoric water is oxidized to W VI O 3 , and as these sediment-water interactions progress, WO 4 2– is formed in the water at pH ~7. Under pH < 7, and sufficient W concentrations, tungstate tends to polymerize, and polymerized species are less likely to adsorb onto sediments. Polymerized species have lower affinity than monomers, which leads to enhanced mobility of W.

58 GEOSCIENCES↗
DOE OSTI2020

Imogolite in water: Simulating the effects of nanotube curvature on structure and dynamics

Imogolite is a fascinating inorganic nanotube that is found in nature or synthesized in a laboratory. The synthesis process is carried out in liquid media, and leads to the formation of almost monodisperse diameter nanotubes. Here we investigate, employing classical molecular dynamics simulations, the interaction of water and imogolite for nanotubes of several radii. We established that water penetrates the pores of N = 9 and larger nanotubes, and adopts a coaxial arrangement in it. Also, while water molecules can diffuse along the center of the nanotube, the molecules next to the inner imogolite walls have very low mobility. At the outer nanotube wall, an increase of water density is observed, this effect extends up to 1 nm, beyond which water properties are bulk-like. Both phenomena are affected by the imogolite curvature.

58 GEOSCIENCES↗
DOE OSTI2020

An inelastic homogenization framework for layered materials with planes of weakness

Many geologic materials have a composite structure, in which macroscopic mechanical behavior is determined by the properties, shape, and heterogeneous distribution of individual constituents. In particular, sedimentary rocks commonly exhibit a layered microstructure, with distinct bedding planes that can also form planes of weakness. In this work, we present a homogenization framework for modeling inelastic layered media. The proposed constitutive model allows for distinct micro-constitutive laws for each layer, explicit representation of layer distributions, as well as incorporation of imperfect bonding at the interface between adjacent layers. No a priori assumptions are needed regarding the specific constitutive models used for the layers and interfaces, providing significant modeling flexibility. The overall framework provides a simple and physically-motivated way of defining anisotropic material behavior as an emergent property of the layered microstructure. The model is calibrated using triaxial and true-triaxial experimental data to demonstrate its ability to describe anisotropic deformation and multiple modes of failure.

58 GEOSCIENCES↗
DOE OSTI2021

Nonlinear convergence in contact mechanics: Immersed boundary finite volume

In this report we present an immersed boundary finite volume (IBM) method for simulating quasistatic contact mechanics of linearly elastic domains at small strains. In IBM, all external boundaries and internal contacts of an object are represented by embedded surfaces inside a Cartesian mesh, which need not conform to the grid lines. The contact constraints consist of the non-penetrability condition and Coulomb’s friction law, which are discretized using special interpolation stencils and enforced via penalty parameters. The resulting nonlinear system depends on displacement unknowns only. To solve it, we use the Newton method but find that it diverges frequently. To understand the divergence pattern, we analyze a simplified 2-cell problem and show that the global convergence of Newton cannot be ensured for any choice of penalty parameters. We thus propose a modified Newton solver, which guarantees convergence for the 2-cell problem and is numerically verified to converge for all the challenging simulations considered herein. While both 1 st - and 2 nd -order variants of IBM, in displacement unknowns, are proposed, the modified Newton solver applies only to the 1 st -order variant.

42 ENGINEERING↗
DOE OSTI2021

Parallel exponential time differencing methods for geophysical flow simulations

Two ocean models are considered for geophysical flow simulations: the multilayer shallow water equations and the multilayer primitive equations. For the former, we investigate the parallel performance of exponential time differencing (ETD) methods, including exponential Rosenbrock–Euler, ETD2wave, and B-ETD2wave. For the latter, we take advantage of the splitting of barotropic and baroclinic modes and propose a new two-level method in which an ETD method is applied to solve the fast barotropic mode. Furthermore, these methods could improve the computational efficiency of numerical simulations because ETD methods allow for much larger time step sizes than traditional explicit time-stepping techniques that are commonly used in existing computational ocean models. Several standard benchmark tests for ocean modeling are performed and comparison of the numerical results demonstrates a great potential of applying the parallel ETD methods for simulating real-world geophysical flows.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Interface PINNs (I-PINNs): A physics-informed neural networks framework for interface problems

Here, we present a novel physics-informed neural networks (PINNs) framework for modeling interface problems, termed Interface PINNs (I-PINNs). I-PINNs uses different neural networks for any two subdomains separated by a sharp interface such that the neural networks differ only through their activation functions while the other parameters remain identical. The performance of I-PINNs, conventional PINNs, and other existing domain-decomposition PINNs methods such as extended PINNs (XPINNs) and multi-domain PINN (M-PINN) is compared through several one-dimensional, two-dimensional, and three-dimensional benchmark elliptic interface problems. The results demonstrate that I-PINNs provides a root-mean-square-error accuracy, at least two orders of magnitude better than conventional PINNs and XPINNs at approximately one-tenth of the computational cost of conventional PINNs and half the cost of XPINNs. Additionally, while I-PINNs and M-PINN provide comparable accuracies, M-PINN is found to be approximately 50% more expensive.

42 ENGINEERING↗
DOE OSTI2024

Pressure stability in explicitly coupled simulations of poromechanics with application to CO 2 sequestration

We study in detail the pressure stabilizing effects of the non-iterated fixed-stress splitting in poromechanical problems which are nearly undrained and incompressible. When applied in conjunction with a spatial discretization which does not satisfy the discrete inf–sup condition, namely a mixed piecewise linear–piecewise constant spatial discretization, the explicit fixed-stress scheme can have a pressure stabilizing effect in transient problems. This effect disappears, however, upon time step refinement or the attainment of steady state. The interpretation of the scheme as an Augmented Lagrangian method similar to Uzawa iteration for incompressible flow helps explain these results. Moreover, due to the slowly evolving solution within undrained seal regions, we show that the explicit fixed-stress scheme requires very large time steps to reveal its pressure stabilizing effect in examples of geologic CO 2 sequestration. We note that large time steps can result in large errors in drained regions, such as the aquifer or reservoir regions of these examples, and can prevent convergence of nonlinear solvers in the case of multiphase flows, which can make the explicit scheme an unreliable source of pressure stabilization. We conclude by demonstrating that pressure jump stabilization is as effective in the explicit fixed-stress setting as in the fully implicit setting for undrained problems, while maintaining the stability and convergence of the fixed-stress split for drained problems.

58 GEOSCIENCES↗
DOE OSTI2020

Assessing the thermal maturity of black shales using vitrinite reflectance: Insights from Devonian black shales in the eastern United States

Thermal maturity of source rocks indicated by vitrinite reflectance (R o ) is an important and reliable parameter to determine the petroleum potential of sedimentary basins. Originally, R o was used to characterize the degree of coalification of coals and thus works well for coal seams, but it has limitations when used to determine the thermal maturity of black shale successions. A suite of six coal-shale pairs from the Upper Devonian black shale formations in the eastern United States (New Albany Shale, Ohio Shale, Dunkirk Shale, and Rhinestreet Shale) was selected to study the applicability of R o in assessing the thermal maturity of black shale successions. The results show that vitrinite in the studied coal samples is dominated by collotelinite, whereas vitrinite in black shales occurs as small dispersed particles (~5 μm) in the mineral matrix. When comparing the size and morphology of dispersed vitrinite particles in shales and collotelinite fragments in coals, vitrinite in shales and adjacent coals should have the same origin. The measured mean random R o of vitrinite in coals ranges from 0.51–0.68%, and is 0.04–0.11% (average 0.07%) lower than that of dispersed vitrinite particles in enclosing shales. This observation contrasts with previously reported R o suppression in liptinite-rich black shales. A high standard deviation of R o measurements indicates a highly heterogeneous nature of vitrinite in black shales. Three mechanisms can be envisioned to contribute to the higher R o of dispersed vitrinite particles in black shales relative to enclosed coals. First, small vitrinite particles may become more oxidized because small particles are more frequently suspended during transport to the site of deposition and reworking of bottom sediments after deposition than large pieces of driftwood that will turn into enclosed coal lenses during burial diagenesis. Second, misidentification of zooclast (e.g., chitinozoan) fragments as vitrinite due to loss of diagnostic morphology. Third, various macerals in the vitrinite group (e.g., corpogelinite and collotelinite) may have had different original reflectance values. Based on the petrographic characteristics of vitrinite and vitrinite-like particles, caution should be applied when using the R o values of dispersed vitrinite and vitrinite-like particles in black shales as indicators of thermal maturity.

58 GEOSCIENCES↗
DOE OSTI2020

Major element composition controls rare earth element solubility during leaching of coal fly ash and coal by-products

Coal combustion ash and pre-combustion coal refuse are currently under consideration as potential sources of rare earth elements. One of the early steps in recovering REEs from coal by-products is often acid leaching, which can result in low pH leachates with complex aqueous chemistry. The aim of this work was to understand the connection between REE solubility, pH, and major elemental components of leachates for coal by-products. To accomplish this, we investigated the effects of solids concentration (i.e., pulp density) and pH adjustment on REE solubility in acid leachates of coal fly ashes from the Powder River Basin (PRB) and Appalachian Basin in the United States, and a coal processing refuse from the Southwestern U.S. For PRB ashes, the concentrations of soluble REEs generally increased with increasing pulp density; however, at pulp density values above 80–100 g/L, the soluble REE concentrations in the leachates were markedly lower. Similarly, the soluble concentrations of other major solutes (Fe, Al, Si) that leached from PRB fly ashes were also non-linear with pulp density. These major elements tended to reach maximum concentration values at 60–70 g/L pulp density. In contrast, for the Appalachian fly ashes and the coal by-product, soluble concentrations of REE and major elements in leachates increased linearly with pulp density. Chemical equilibria calculations of mineral saturation indices indicated that trends in soluble REE concentrations could be explained by saturation conditions for Fe and Al-(hydr)oxides and possibly sulfate minerals, but not lanthanide hydroxides. Furthermore, pH adjustment of the acid leachates showed that REEs and many major solutes were removed from solution at pH values above 4.5, also consistent with Fe- and Al-(hydr)oxide precipitation. These results highlight the importance of understanding the chemical composition of leachates when designing REE recovery processes for low-grade geologic feedstocks and that precipitation of hydr(oxide) or sulfate minerals of major elements rather than discreet formation of REE mineral phases could be used for process optimization.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2022

Micro- to nano-scale areal heterogeneity in pore structure and mineral compositions of a sub-decimeter-sized Eagle Ford Shale

Mineral and organic matter compositions & pore structures of fine-grained shale influence reservoir properties. To improve the understanding of spatial heterogeneity in core-sized samples, methods of microscale X-ray fluorescence (μXRF) mapping, (ultra-) small-angle x-ray scattering [(U)SAXS] and wide-angle X-ray scattering (WAXS) have been used to determine elemental, pore-structure variations at scales up to ~10 cm on two samples prepared at circular and rectangular orientations from a piece of Eagle Ford Shale outcrop in South Texas, USA. In addition, thin section petrography and field emission-scanning electron microscopy observations, X-ray diffraction (XRD), total organic carbon, and pyrolysis were utilized to investigate the potential spatial heterogeneity of pore types, mineral and organic matter compositions for cm-sized samples at both orientations. Overall, the siliceous-carbonate mineral contents in these two samples (8 cm×8 cm×0.08 cm and 5 cm × 8 cm × 0.08 cm, in terms of width×length×thickness) of carbonate-rich Eagle Ford Shale vary between laminations at mm scales. For the circular sample, porosity and specific surface area (SSA) variations range from 0.82 to 3.04% and 1.51 to 14.1 m 2 /g, respectively. For the rectangular sample, values for porosity and SSA vary from 0.93 to 2.50% and 3.95 to 10.8 m 2 /g. By analyzing six selected sub-samples on each of two samples with (U)SAXS and XRD techniques, nm-sized pores are mainly interparticle ones in the higher calcite regions, where the porosity is also relatively lower, while the lower calcite regions consist of both interparticle and intraparticle pore types with higher porosity. Lastly, the μXRF and (U)SAXS mappings are combined to generate porosity distribution maps to provide more insights about sample heterogeneity related to the laminations and fractures at our observational scales.

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↗