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At least 1,405 records · Page 78
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Reduction and potential remediation of U(VI) by dithionite at an in-situ recovery mine: Insights gained by δ 238 U

In-situ recovery is a common method of mining U ore. This technique involves injecting an oxidant to oxidize U deposited as insoluble U(IV) to soluble U(VI) and a complexing agent to form mobile U(VI) compounds, which are extracted from mining waters. Unfortunately, U concentrations often remain elevated in groundwater following this mining process. One promising technique to decrease U concentrations to acceptable levels is in-situ remediation where a reductant is injected into the mined area to reduce U(VI) back to insoluble U(IV). Here we assess the efficacy of the chemical reductant dithionite to reduce U(VI) concentrations. While dithionite can reduce environmental Cr(VI), dithionite has previously never been tested for reducing U(VI) in the environment. We determine how effectively dithionite remediates U(VI) contamination using aqueous U concentration and δ 238 U data. U concentrations and δ 238 U decrease during the dithionite experiment, demonstrating that dithionite induces U(VI) reduction. As dithionite is removed by pumping, U concentrations and δ 238 U increase towards background levels, but U(VI) reduction continues for an extended period. In conclusion, measurements demonstrate that re-oxidation and remobilization does not appear to occur due to the reducing condition of groundwater.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Assembly of polyelectrolyte star block copolymers at the oil–water interface

To understand and resolve adsorption, reconfiguration, and equilibrium conformations of charged star copolymers, we carried out an integrated experimental and coarse-grained molecular dynamics simulation study of the assembly process at the oil–water interface. This is important to guide development of novel surfactants or amphiphiles for chemical transformations and separations. The star block copolymer consisted of arms that are comprised of hydrophilic–hydrophobic block copolymers that are covalently tethered via the hydrophobic blocks to one point. The hydrophobic core represents polystyrene (PS) chains, while the hydrophilic corona represents quaternized poly(2-vinylpyridine) (P2VP) chains. The P2VP is modeled to become protonated when in contact with an acidic aqueous phase, thereby massively increasing the hydrophilicity of this block, and changing the nature of the star at the oil–water interface. This results in a configurational change whereby the chains comprising the hydrophilic corona are significantly stretched into the aqueous phase, while the hydrophobic core remains solubilized in the oil phase. In the simulations, we followed the kinetics of the anchoring and assembly of the star block copolymer at the interface, monitoring the lateral assembly, and the subsequent reconfiguration of the star via changes in the interfacial tension that varies as the degree-of-protonation increases. At low fractions of protonation, the arm cannot fully partition into the aqueous side of the interface and instead interacts with other arms in the oil phase forming a network near the interface. These insights were used to interpret the non-monotonic dependence of pH with the asymptotic interfacial tension from pendant drop tensiometry experiments and spectral signatures of aromatic stretches seen in vibrational sum frequency generation (SFG) spectroscopy. We describe the relationship of interfacial tension to the star assembly via the Frumkin isotherm, which phenomenologically describes anti-cooperativity in adsorbing stars to the interface due to crowding. Although our model explicitly considers long-range electrostatics, the contribution of electrostatics to interfacial tension is small and brought about by strong counterion condensation at the interface. Finally, these results provide key insights into resolving the adsorption, reconfiguration, and equilibrium conformations of charged star block copolymers as surfactants.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Molecular-based analysis of nanoparticle solvation: Classical density functional approach

Proper statistical mechanics understanding of nanoparticle solvation processes requires an accurate description of the molecular structure of the solvent. Achieving this goal with standard molecular dynamics (MD) simulation methods is challenging due to large length scales. An alternative approach to this problem can be formulated using classical density functional theory (cDFT), where a full configurational description of the positions of all the atoms is replaced by collective atomic site densities in the molecule. Using an example of the negatively charged silica-like system in an aqueous polar environment represented by a two-site water model, we demonstrate here that cDFT can reproduce MD data at a fraction of the computational cost. An important implication of this result is the ability to understand how the solvent molecular features may affect the system’s properties at the macroscopic scale. A concrete example highlighted in this work is the analysis of nanoparticle interactions with sizes of up to 100 nm in diameter.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Wet Waste Hydrothermal Liquefaction and Biocrude Upgrading to Hydrocarbon Fuels (2019 State of Technology)

Each year, the DOE Bioenergy Technologies Office (BETO) assesses progress in their research and development efforts toward sustainable production of renewable fuels. Technical and cost targets were previously established for the wet waste hydrothermal liquefaction and biocrude upgrading pathway and summarized in a design report. The present report summarizes the research and associated techno-economic analysis (TEA) in support of the 2019 state of technology (SOT) assessment for this pathway. Data from Pacific Northwest National Laboratory’s Conversion hydrothermal liquefaction (HTL) program for wet waste was used to update the pathway techno-economic analysis (TEA) for the fiscal year 2019 State of Technology (2019 SOT). An overview of the current process model, experimental data and plant economics for the SOT is presented.

09 BIOMASS FUELS↗
DOE OSTI2025

Direct ink writing of aqueous-based Gadolinium (III) oxide slurries

Gadolinium (III) oxide (gadolinia, Gd 2 O 3 ) has recently been identified as an intriguing material for applications in the medical, solid oxide fuel cell, and nuclear industries. This interest drives the need for developing and understanding manufacturing techniques that can produce dense Gd 2 O 3 structures. Direct ink writing (DIW), an extrusion-based additive manufacturing method, has also garnered interest because of its capability to produce dense ceramic parts with increased complexity in an economical manner. In this study, DIW was explored as a manufacturing technique for Gd 2 O 3 . Experiments were performed to develop Gd 2 O 3 bearing inks capable of being processed via DIW. Ink solids loading and sintering temperatures were varied to assess their impact on the final density and microstructure. Optimum sintering conditions are proposed and were experimentally verified at a dwell temperature of 1500°C. Gd 2 O 3 samples were successfully manufactured using DIW, achieving densities greater than 96 % of the theoretical density.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Accelerating Embedding Potential Optimization by Reconstructing the Pseudo-Valence Electron Density

Density functional embedding theory (DFET) enables use of electronic structure methods with higher accuracy than density functional theory in a local region, with applications thus far ranging from (photo/electro)catalysis to reactions in solution. DFET partitions a large collection of atoms into smaller groups that interact via a shared embedding (interaction) potential V emb , determined via functional optimization. The optimized effective potential (OEP) process used to optimize V emb is time-consuming and becomes a computational bottleneck due to sharp, oscillating features of V emb near nuclei. Here, similar to pseudopotential theory, by reconstructing electron densities used in the OEP process from smoother pseudo-valence-only (PVO) electron densities as proxies for total densities of the full system and subsystems, we can retain accuracy in the embedded electronic structure calculations while potentially reducing the overhead of V emb construction, within the projector augmented-wave (PAW) formalism. We explore three different chemical reactions as exemplars to test PVO–DFET, namely, H 2 dissociative adsorption on a Cu(111) surface, H 2 O adsorption on a Pt(111) surface, and aqueous [Ca 2+ –SO 4 2– ] ion-pair formation. The PVO approximation works well for all three systems with minimal loss of accuracy (∼10–70 meV error relative to the original exact-derivative (ED) approach) while accelerating V emb generation for the Cu and Pt systems respectively by 20× and 5×. Given proper numerical convergence parameters, the spatial distributions of differences between PVO- and ED-based V emb outside the core regions are small, explaining the exceptional agreement between the two approaches. Finally, we anticipate that this more efficient PVO–DFET approximation will be useful whenever computation of V emb is much more expensive than subsequent embedded high-level electron correlation calculations.

approximation↗
DOE OSTI2023

Real-Time Nitrate Ion Monitoring with Poly(3,4-ethylenedioxythiophene) (PEDOT) Materials

Nitrate (NO 3 ) pollution in groundwater, caused by various factors both natural and synthetic, contributes to the decline of human health and well-being. Current techniques used for nitrate detection include spectroscopic, electrochemical, chromatography, and capillary electrophoresis. It is highly desired to develop a simple cost-effective alternative to these complex methods for nitrate detection. Therefore, a real-time poly (3,4-ethylenedioxythiophene) (PEDOT)-based sensor for nitrate ion detection via electrical property change is introduced in this study. Vapor phase polymerization (VPP) is used to create a polymer thin film. Variations in specific parameters during the process are tested and compared to develop new insights into PEDOT sensitivity towards nitrate ions. Through this study, the optimal fabrication parameters that produce a sensor with the highest sensitivity toward nitrate ions are determined. With the optimized parameters, the electrical resistance response of the sensor to 1000 ppm nitrate solution is 41.79%. Furthermore, the sensors can detect nitrate ranging from 1 ppm to 1000 ppm. The proposed sensor demonstrates excellent potential to detect the overabundance of nitrate ions in aqueous solutions in real time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Reactive transport modeling for supporting climate resilience at groundwater contamination sites

Abstract. Climate resilience is an emerging issue at contaminated sites and hazardous waste sites, since projected climate shifts (e.g., increased/decreased precipitation) and extreme events (e.g., flooding, drought) could affect ongoing remediation or closure strategies. In this study, we develop a reactive transport model (Amanzi) for radionuclides (uranium, tritium, and others) and evaluate how different scenarios under climate change will influence the contaminant plume conditions and groundwater well concentrations. We demonstrate our approach using a two-dimensional (2D) reactive transport model for the Savannah River Site F-Area, including mineral reaction and sorption processes. Different recharge scenarios are considered by perturbing the infiltration rate from the base case as well as considering cap-failure and climate projection scenarios. We also evaluate the uranium and nitrate concentration ratios between scenarios and the base case to isolate the sorption effects with changing recharge rates. The modeling results indicate that the competing effects of dilution and remobilization significantly influence pH, thus changing the sorption of uranium. At the maximum concentration on the breakthrough curve, higher aqueous uranium concentration implies that sorption is reduced with lower pH due to remobilization. To better evaluate the climate change impacts in the future, we develop the workflow to include the downscaled CMIP5 (Coupled Model Intercomparison Project) climate projection data in the reactive transport model and evaluate how residual contamination evolves through 2100 under four climate Representative Concentration Pathway (RCP) scenarios. The integration of climate modeling data and hydrogeochemistry models enables us to quantify the climate change impacts, assess which impacts need to be planned for, and therefore assist climate resiliency efforts and help guide site management.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2006

The Rocks of the Columbia Hills

The Mars Exploration Rover Spirit has identified five distinct rock types in the Columbia Hills of Gusev crater. Clovis Class rock is a poorly-sorted clastic rock that has undergone substantial aqueous alteration. We interpret it to be aqueously-altered ejecta deposits formed by impacts into basaltic materials. Wishstone Class rock is also a poorly-sorted clastic rock that has a distinctive chemical composition that is high in Ti and P and low in Cr. Wishstone Class rock may be pyroclastic in origin. Peace Class rock is a sedimentary material composed of ultramafic sand grains cemented by significant quantities of Mg- and Ca-sulfates. Peace Class rock may have formed when water briefly saturated the ultramafic sands, and evaporated to allow precipitation of the sulfates. Watchtower Class rocks are similar chemically to Wishstone Class rocks, and have undergone widely varying degrees of near-isochemical aqueous alteration. They may also be ejecta deposits, formed by impacts into Wishstone-rich materials and altered by small amounts of water. Backstay Class rocks are basalt/trachybasalt lavas that were emplaced in the Columbia Hills after the other rock classes were, either as impact ejecta or by localized volcanic activity. The geologic record preserved in the rocks of the Columbia Hills reveals a period very early in martian history in which volcanic materials were widespread, impact was a dominant process, and water was commonly present.

Squyres, Steven W.↗
DOE OSTI2025

SaltStone Wastewater Cement Study Using Isothermal Calorimetry, Standard Concrete Characterization Techniques, and CemGEMS - 25169

Cementitious reagents are used to solidify/stabilize aqueous radioactive, hazardous, and mixed salt solutions, and sludges to meet low-level radioactive waste (LLW) and Resource Conservation and Recovery Act (RCRA) requirements for disposal at Department of Energy (DOE). It is flexible enough to solidify radioactive wastewater saturated in complex species that include but are not limited to radioactive isotopes from the bombardment of neutrons in reactor operation, corrosion products from metallic components, and a variety of soluble organic compounds. [1,2]. Waste form testing typically includes processing or fresh properties, cured properties, compressive strength and hydraulic properties, porosity, density, saturated and unsaturated moisture transport, and leachability of contaminants in the waste form pore solution. Properties are collected over a relatively limited time, typically 28 to 365 days [3]. In addition, changes in the waste form as the result of time and changing conditions are important for concrete engineers to predict overall performance of the forms and potential release of contaminants in the disposal process via unintended filtration into the environment [4]. These predictions are determined/calculated characterizing young waste forms (relative to the standard age of concrete) and are based on transport through soluble ions in pore solutions. Characterization methods include X-ray, SEM, and isothermal calorimetry among other methods used to define the composition, amorphous vs. crystalline nature of the components, and the energetic formation mechanisms for multi-phase mineral systems. [5–7] Isothermal calorimetry is a well standardized technique for cements and concretes and can be used to predict the timing and nature of the hydration reactions.[8] The technique can measure long term energetic

Bustamante, Michael E. [Savannah River National La↗
DOE OSTI2023

Using Aggregation to Chaperone Nanoparticles Across Fluid Interfaces

Nanoparticles (NPs) transfer is usually induced by adding ligands to modify NP surfaces, but aggregation of NPs oftentimes hampers the transfer. Here, we show that aggregation during NP phase transfer does not necessarily result in transfer failure. Using a model system comprising gold NPs and amphiphilic polymers, we demonstrate an unusual mechanism by which NPs can undergo phase transfer from the aqueous phase to the organic phase via a single-aggregation-single pathway. Our discovery challenges the conventional idea that aggregation inhibits NP transfer and provides an unexpected pathway for transferring larger-sized NPs (>20 nm). The charged amphiphilic polymers effectively act as chaperons for the NP transfer and offer a unique way to manipulate the dispersion and distribution of NPs in two immiscible liquids. Moreover, by intentionally jamming the NP-polymer assembly at the liquid/liquid interface, the transfer process can be inhibited.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Electrochemically Assisted Single Crystal Growth of Reduced Preyssler Polyoxometalates Decorated with M 2+ ( M = Co, Ni) and Cubane–Like Ni 4 O 4 Units

Polyoxometalates (POMs) are of great interest to the scientific community, and their reduction and nucleation have been well–established by multi–step techniques. The present study develops an electrochemical approach for simultaneous reduction and nucleation of polyoxometalate–containing solids. Herein we report crystal growth of reduced Preyssler polyoxotungstate–based (anionic formula [NaP 5 W 30 O 110 ] 14– ) new crystalline solids made of Preyssler anions interlinked by Co 2+ and Ni 2+ ions. Crystal nucleation and in situ reduction were achieved at room temperature using a two silver wire electrode setup in various aqueous solutions under constant applied potentials. The POM material was deposited on the cathode, and its structure was characterized by X–ray diffraction techniques. The primary structure type observed involves POMs decorated by disordered Co 2+ /Ni 2+ octahedra and fused into 1–D pillars by additional Co 2+ /Ni 2+ octahedra. Additionally, a secondary phase was observed in the Ni–based reactions, where reduced Preyssler anions are decorated by Ni 4 O 4 cubane–like units. To understand the electrochemical process, polarization curves of the electrolyte solutions are presented, suggesting an applied potential best suited for crystal growth. The work highlights the effectiveness of an electrochemical pathway where nucleation and simultaneous reduction of POMs can make novel reduced POM solids.

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

Bulk Anion Recognition Kinetically Holds Back Interfacial Adsorption

The competition between bulk and interfacial phenomena underlies many key processes in complex chemical phenomena and transport. While competitive processes are often framed in a thermodynamic context, opportunities to leverage transient species found away from equilibrium can provide a kinetic handle to achieve unconventional reaction outcomes. In this work, we outfit an iminoguanidinium headgroup capable of selective SO 4 2– complexation with alkyl tails of varying complexity to probe competitive bulk and interfacial reaction pathways and tune kinetic pathways for selective chemical separations. Using sum frequency generation (SFG) vibrational spectroscopy we unexpectedly find that adsorption of ligands to the air–aqueous interface was dramatically slowed down for species with increasingly hydrophobic tails. Underlying this phenomenon, we show that the formation of bulk colloidal species with differing propensities for SO 4 2– inhibited surface adsorption via a kinetic bottleneck in the exchange of molecular extractants with colloidal aggregates. This kinetic effect could open up avenues to access unconventional selectivity via complexation of strongly coordinating species in the bulk phase, allowing for more weakly coordinating species to transport via interfacial mechanisms. Furthermore, this work broadly probes nonequilibrium phenomena in chemical separations that arise through unexpected interfacial events that are neglected in traditional equilibrium descriptions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2000

Convection Induced by High Frequency Rotating Magnetic Field in Ionic Aqueous Solutions

Rotating magnetic fields (RMF) have found applications in modern metallurgy. Examples are casting and semiconductor crystal growth technology. Rotating convective flows can also be induced in ionic fluids. Due to optical transparency, these fluids offer a great opportunity to visualize convection. In this work, we investigate the dynamics of convection induced by a high frequency (100 kHz range) RMF. A dye injected into a cylindrical column of salty water serves as an indicator of the flow. The developed technique has been used to study mixing phenomena induced by a RMF both when the direc'tion of the field rotation is constant and when it is alternated. Optical recording has been used to analyze this process. A numerical model describing RMF mixing in the laminar regime will also be presented.

Volz, Martin P.↗
DOE OSTI2022

Plutonium reactive transport in fractured granite: Multi-species experiments and simulations

Plutonium (Pu) in the subsurface environment can transport in different oxidation states as an aqueous solute or as colloidal particles. The transport behavior of Pu is affected by the relative abundances of these species and can be difficult to predict when they simultaneously exist. This study investigates the concurrent transport of Pu intrinsic colloids, Pu(IV) (aq) and Pu(V-VI) (aq) through a combination of controlled experiments and semi-analytical dual-porosity transport modeling. Pu transport experiments were conducted in a fractured granite at high and low flow rates to elucidate sorption processes and their scaling behavior. In the experiments, Pu(IV) (aq) was the least mobile of the Pu species, Pu(V-VI) (aq) had intermediate mobility, and the colloidal Pu, which consisted mainly of precipitated and/or hydrolyzed Pu(IV), was the most mobile. The semi-analytical modeling revealed that the sorption of each Pu species was rate-limited, as the sorption could not be described by assuming local equilibrium in the experiments. The model was able to describe the sorption of the different Pu species that occurring either on fracture surfaces, in the pores of the rock matrix, or simultaneously in both locations. While equally good fits to the data could be achieved using any of these assumptions, a fracture-dominated process was considered to be the most plausible because it provided the most reasonable estimates of sorption rate constants. Importantly, a key result of this work is that the sorption rate constant of all Pu species tends to decrease with increasing time scales, which implies that Pu will tend to be more mobile at longer time scales than observations at shorter time scales suggest. This result has important implications for predicting the environmental impacts of Pu in the safety assessments of geologic repositories for radioactive waste disposal, and we explore potential mechanistic bases for upscaling the sorption rate constants to time and distance scales that cannot be practically evaluated in experiments.

58 GEOSCIENCES↗
DOE OSTI2021

Electrochemical Reductive N-Methylation with CO 2 Enabled by a Molecular Catalyst

The development of benign methylation reactions utilizing CO 2 as a one-carbon building block would enable a more sustainable chemical industry. Electrochemical CO 2 reduction has been extensively studied, but its application for reductive methylation reactions remains out of the scope of current electrocatalysis. Here, in this work, we report the first electrochemical reductive N-methylation reaction with CO 2 and demonstrate its compatibility with amines, hydroxylamines, and hydrazine. Catalyzed by cobalt phthalocyanine molecules supported on carbon nanotubes, the N-methylation reaction proceeds in aqueous media via the chemical condensation of an electrophilic carbon intermediate, proposed to be adsorbed or near-electrode formaldehyde formed from the four-electron reduction of CO 2 , with nucleophilic nitrogenous reactants and subsequent reduction. By comparing various amines, we discover that the nucleophilicity of the amine reactant is a descriptor for the C-N coupling efficacy. We extend the scope of the reaction to be compatible with cheap and abundant nitro-compounds by developing a cascade reduction process in which CO 2 and nitro-compounds are reduced concurrently to yield N-methyl amines with high mono-methylation selectivity via the overall transfer of 12 electrons and 12 protons.

amines↗
DOE OSTI2020

Actinide N-Donor Thermodynamics: Expanding the f-element Covalency Dialogue. Final report

Resolving the chemistry and physics of f-electrons is one of the grand challenges of science for energy technology. A central component of this challenge is describing covalency in actinide-ligand interactions. Crystallography, x-ray spectroscopy and computational techniques have provided reasonable, and in some cases remarkable, support for covalency in actinide-ligand interactions. Courtesy the quality of the results obtained, a significant portion of the covalency dialogue has been forwarded through solid-state and computational studies of the more stable actinides (Th, U, Pu, Np). However; recent reports have questioned whether covalency in actinide interactions increases or decreases across the series. Examination of less-stable trans-actinides (Am, Cm, Bk, Cf and Es) by the aforementioned approaches can be rapidly limited due to material availability, radiological hazards and experimental data to validate computational models. Furthermore, limited thermodynamic data exists to confirm covalency in actinide solution phase interactions that are highly relevant to the remediation and reprocessing of used nuclear fuel. The best-defined interactions of actinides with soft donors in aqueous solutions involve (poly)aminopolycarboxylate (APC) ligands. The chelate effect and binding affinity with the acetic acid APCs subgroups encourages amine interactions with the actinide metal center. In the absence of these factors, amine interactions with actinides are too weak to overcome the protective hydration shell of the dissolved ion. The ability for APCs to force actinide interactions with soft nitrogen donors (as defined by Pearson’s Hard Soft Acid Base theory) encourages the application of these ligands in a variety of processes for actinide recovery from nearly chemically identical lanthanides. The ability to functionalize the amine center of the ligand in a variety of capacities (adding additional amine groups, exchanging the conventional acetate group for an acetate group, etcetera), allows for the APC ligand to serve as a thermodynamic probe for actinide-nitrogen interactions. Perhaps the single most significant breakthrough during the previous funding cycle was the observation that covalency for the transplutonium part of the actinide series can be increasingly influenced with energy degeneracy driven covalency as the actinides become heavier. This was observed most predominantly with dipicolinic acid, but extensions of f-orbital degeneracy were found to affect aliphatic aminopolycarboxylate-actinide complexes through einsteinium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗