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At least 1,711 records · Page 95

Results for the January 2023 Semiannual Tank 50 Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the January 2023 Semiannual sample of Tank 50 salt solution are presented in tabulated form. The information from this characterization will be used by Savannah River Mission Completion (SRMC) for the transfer of aqueous waste from Tank 50 to the Saltstone Production Facility (SPF), where the waste will be treated and disposed in the Saltstone Disposal Facility. This Technical Report compares results, where applicable, to SPF Waste Acceptance Criteria (WAC) LIMITS and TARGETS that were established at the time the Tank 50 sample was obtained.1 The chemical and radionuclide contaminant results from the characterization of the January 2023 semiannual sampling of Tank 50 were requested by SRMC personnel via a Task Technical Request (TTR)2 and details of the testing are presented in the Savannah River National Laboratory (SRNL) Task Technical and Quality Assurance Plan (TTQAP).3 This Technical Report is part of Deliverable 2 relating to Task 1 from the SRMC request.2 Data pertaining to the regulatory limits for Resource Conservation and Recovery Act (RCRA) metals per Task 2 from the SRMC request will be obtained semiannually for the January 2023 and July 2023 Tank 50 samples.

Crawford, Charles L.↗

The promise of optical NMR spectroscopy for experimental aqueous geochemistry

Here, we discuss new quantum technologies being adapted to detect extraordinarily small magnetic fields. The signals are derived from the stimulated emission of light from single-atom defects in diamonds. The intensity of light reports the spin state of the electrons in the color center. The physics is relevant to geochemists because it points to a means of conducting NMR experiments on solutions in diamond-anvil cells. Because the method is so sensitive, it can detect signals in subnanoliter volumes, making work at elevated temperatures and pressures possible, and also on solutions that are dangerous in larger volumes.

58 GEOSCIENCES↗

Aqueous harvesting of 88 Zr at a radioactive-ion-beam facility for cross-section measurements

Isotope harvesting is a method of collecting the long-lived radioisotopes that build up during the operation of ion-beam facilities in a way that is useful for subsequent research. As a demonstration of this method for the collection of a group IV metal at a fragmentation facility, the high-energy Zr 88 secondary beam produced from a 140-MeV/u Mo 92 primary beam at the National Superconducting Cyclotron Laboratory (NSCL) was stopped in a water target. The setup aimed to mimic the aqueous beam dump that will be implemented at the Facility for Rare Isotope Beams (FRIB). The collected Zr 88 and accompanying Y 88 decay daughter were radiochemically extracted from the solution and made into target samples suitable for neutron-capture cross-section measurements. These samples were then irradiated at two reactor facilities, and the Zr 88 average thermal-neutron-capture cross section ( σ T ) and resonance integral ( I ) were determined to be σ T = ( 8.04 ± 0.63 ) × 10 5 b and I = ( 2.53 ± 0.28 ) × 10 6 b. The σ T value agrees well with previous results and I , determined for the first time here, was found to be the largest measured resonance integral by two orders of magnitude. The Y 88 thermal-neutron-capture cross section was determined to be less than 1.8 × 10 4 b. This work demonstrates the steps needed to make cross-section measurements with samples produced via aqueous isotope harvesting.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Aqueous Chemical Modeling of Sedimentation on Early Mars with Application to Surface-Atmosphere Evolution

This project was to investigate models for aqueous sedimentation on early Mars from fluid evaporation. Results focused on three specific areas: (1) First, a fluid evaporation model incorporating iron minerals was developed to compute the evaporation of a likely solution on early Mars derived from the weathering of mafic rock. (2) Second, the fluid evaporation model was applied to salts within Martian meteorites, specifically salts in the nakhlites and ALH84001. Evaporation models were found to be consistent with the mineralogy of salt assemblages-anhydrite, gypsum, Fe-Mg-Ca carbonates, halite, clays-- and the concentric chemical fractionation of Ca-to Mg-rich carbonate rosettes in ALH84001. We made progress in further developing our models of fluid concentration by contributing to updating the FREZCHEM model. (3) Third, theoretical investigation was done to determine the thermodynamics and kinetics involved in the formation of gray, crystalline hematite. This mineral, of probable ancient aqueous origin, has been observed in several areas on the surface of Mars by the Thermal Emission Spectrometer on Mars Global Surveyor. The "Opportunity" Mars Exploration Rover has also detected gray hematite at its landing site in Meridiani Planum. We investigated how gray hematite can be formed via atmospheric oxidation, aqueous precipitation and subsequent diagenesis, or hydrothermal processes. We also studied the geomorphology of the Aram Chaos hematite region using Mars Orbiter Camera (MOC) images.

Catling, David C.↗

The Interplay of Solvation and Polarization Effects on Ion Pairing in Nanoconfined Electrolytes

The nature of ion–ion interactions in electrolytes confined to nanoscale pores has important implications for energy storage and separation technologies. However, the physical effects dictating the structure of nanoconfined electrolytes remain debated. Here we employ machine-learning-based molecular dynamics simulations to investigate ion–ion interactions with density functional theory level accuracy in a prototypical confined electrolyte, aqueous NaCl within graphene slit pores. We find that the free energy of ion pairing in highly confined electrolytes deviates substantially from that in bulk solutions, observing a decrease in contact ion pairing but an increase in solvent-separated ion pairing. These changes arise from an interplay of ion solvation effects and graphene’s electronic structure. Notably, the behavior observed from our first-principles-level simulations is not reproduced even qualitatively with the classical force fields conventionally used to model these systems. The insight provided in this work opens new avenues for predicting and controlling the structure of nanoconfined electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lamellar and Hexagonal Assemblies of PEG-Grafted Silver Nanoparticles: Implications for Plasmonics and Photonics

Assembly of silver nanoparticles (AgNPs) grafted with thiolated poly(ethylene glycol) (PEG-SH) with various molecular weights is reported. Synchrotron-based X-ray surface-sensitive diffraction methods are used to determine the nature of two-dimensional (2D) assemblies at liquid/vapor interfaces, and small-angle X-ray scattering (SAXS) is used to monitor the three-dimensional (3D) assemblies in bulk suspensions. We find that assembly can be induced either by the addition of K 2 CO 3 or polyacrylic acid (PAA) to the PEG-AgNP aqueous suspensions. The addition of K 2 CO 3 induces a 2D hexagonal structure at the liquid/vapor interface and a 3D hexagonal columnar structure in solutions, where the columns consist of tethered PEG-AgNP chains. On the other hand, the addition of PAA leads to the formation of a 2D lamella-like distorted hexagonal sheet at the liquid/vapor interface and a 3D lamellar superstructure formed by stacked 2D sheets in the PEG-AgNP suspension. Effects of the core type of nanoparticles on the assembly can be used to control structures for potential applications in plasmonics and photonics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating Polymer Properties with Different Additives for Carbon Capture and Other Applications

Anthropogenic climate change is one of this generation’s most pressing concerns, with the potential to completely alter the delicate balance we’ve struck with nature. Already, global temperatures have risen 1.29°C, leading to disrupted weather systems, extinctions, increased risks of wildfires, and sea level rise, to name a few effects. Carbon dioxide emission from the combustion of fossil fuels and other industrial activity is a large driver of this phenomenon, as it absorbs heat before it can be radiated away from Earth, trapping it. Carbon dioxide has reached unprecedented levels in our atmosphere, showing a 50% increase from preindustrial averages to a whopping 430 ppm. Thus, reducing the amount of carbon dioxide via carbon capture technology is an important endeavor that serves to benefit everyone. The Microencapsulated CO 2 Sorbent (MECS) team at Lawrence Livermore National Laboratory (LLNL) has turned to microencapsulation to approach this endeavor. Microcapsules provide an attractive approach to carbon capture, combining large surface areas for more efficient mass transfer, regenerative abilities, reduced solvent loss, and improved handling. Additionally, while existing carbon capture technology relies on industrial plants, capsules could present a modular approach to carbon capture, reducing the need for extensive physical infrastructure. The MECS team’s design consists of a polymer membrane that contains a liquid carbon sequestering sorbent, aqueous sodium carbonate. The carbon capturing reaction occurs in three distinct steps, the first of which is the dissolution of carbon dioxide into the sorbent solution and its conversion into carbonic acid (H 2 CO 3 ), shown in equations 1 and 2 respectively. Because this step hinges upon the ability of carbon dioxide to reach the solution inside the capsule, it is necessary that the microcapsule shell is permeable to carbon dioxide gas. The MECS team produces these microcapsules using the in-air droplet encapsulation apparatus (IDEA) shown in figure 1, which can produce uniform micron-scale droplets at speeds much faster than traditional single-dispersal microfluidic-based techniques. The IDEA Is 100 times faster than these current techniques and can reach up to 1000 times their speed when incorporating a multi-nozzle design. Additionally, because droplets are produced in-air via vibration, IDEA can decrease post-processing times and material waste by 99% and can fabricate microgels that are 10 to 100 times more viscous than can be produced via traditional microfluidics. While this design represents a breakthrough in the throughput, efficiency, and tunability of microcapsule production, it imposes a major constraint on the microcapsule curing process. Because microcapsule shells are crosslinked with UV light while falling 30 cm through the air, this gives them a reaction window of approximately 0.2 seconds. Thus, the system and shell formulations must be optimized such that the shells can be fully crosslinked within this very narrow window, prompting investigations into curing behavior.

36 MATERIALS SCIENCE↗

Structure and energetics of model amphiphilic molecules at the water liquid-vapor interface - A molecular dynamics study

A molecular dynamics study of adsorption of p-n-pentylphenol at infinite dilution at the water liquid-vapor interface is reported. The calculated free energy of adsorption is -8.8 +/- 0.7 kcal/mol, in good agreement with the experimental value of -7.3 kcal/mol. The transition between the interfacial region and the bulk solution is sharp and well-defined by energetic, conformational, and orientational criteria. At the water surface, the phenol head group is mostly immersed in aqueous solvent. The most frequent orientation of the hydrocarbon tail is parallel to the interface, due to dispersion interactions with the water surface. This arrangement of the phenol ring and the alkyl chain requires that the chain exhibits a kink. As the polar head group is being moved into the solvent, the chain length increases and the tail becomes increasingly aligned toward the surface normal, such that the nonpolar part of the molecule exposed to water is minimized. The same effect was achieved when phenol was replaced by a more polar head group, phenolate.

Pohorille, Andrew↗

A New Optical Scheme for a Polarimetric-Based Glucose Sensor

We describe a new optical scheme to perform polarimetric measurements to detect glucose concentration in the aqueous humor of a model eye. The ultimate aim is to apply this technique in designing a new instrument for measuring glucose levels in diabetic patients routinely, frequently, and non-invasively. The scheme exploits the Brewsterreflection of circularly polarized light off of the lens of the eye. Theoretically, this backreflected linearly polarized light on its way to the detector is expected to rotate its state of polarization due to the presence of glucose molecules in the aqueous humor of patients. An experimental laboratory setup based on this scheme was designed and tested by measuring a range of known concentration of glucose solutions dissolved in water.

Ansari, Rafat R.↗

Laboratory Simulations of Ammonia-Rich Oceans in Icy Worlds

Improved equations of state for ammonia-water solutions are important for properly understanding the interiors of large icy satellites hosting deep interior oceans. Titan is the primary example of such a world, but water-rich dwarf planets Measurements of solution density are now possible at relevant pressures (above approx. 250 megapascals) using the Simulator for Icy World Interiors. Analysis of sound velocity measurements in aqueous magnesium sulfate obtained in our laboratory, shows a correction on the order of 5% to 700 megapascals (7 kilobar) from -20 to 100 C and to 3 m (approx. 30 percentage by weight) concentration. Accurate prediction of density as a function of pressure, temperature, and ammonia concentration are needed for interpretation of remote observations to address questions of interior liquid layer depth, composition, and fluid dynamics.

equations of state↗

Effect of hydrophobic ionic liquids aqueous solubility on metal extraction from hydrochloric acid media: Mathematical modelling and trivalent thallium behavior

A mathematical model to explain cations’ solubility of both protic and aprotic ionic liquids in a wide range of hydrochloric acid solutions has been developed. The concept of this model is based on an assumption of the mineral acid extraction into the organic phase, formation of a salt there between an ionic liquid cation and chloride-anion due to ions recombination and partial salt back-extraction. The proposed approach allows estimating corresponding extraction constants. Comparison of calculated and experimentally measured solubility product constants shows that they are in good agreement. It has been determined also that the more the hydrophilicity of the ionic liquids’ cation the more hydrochloric acid is extracted. Furthermore, this model has been utilized to facilitate analysis of thallium transfer into hydrophobic ionic liquids providing insights into the mechanism of metal extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The effect of heat treatment and test parameters on the aqueous stress corrosion cracking of D6AC steel

The crack growth behavior of D6AC steel as a function of stress intensity, stress and corrosion history and test technique, under sustained load in natural seawater, 3.3 percent NaCl solution, distilled water, and high humidity air was investigated. Reported investigations of D6AC were considered with emphasis on thermal treatment, specimen configuration, fracture toughness, crack-growth rates, initiation period, threshold, and the extension of corrosion fatigue data to sustained load conditions. Stress history effects were found to be most important in that they controlled incubation period, initial crack growth rates, and apparent threshold.

Gilbreath, W. P.↗

Brewster angle-cavity ringdown spectroscopy for low temperature plasma measurements in multiphases

Here we report on the development of a Brewster angle-cavity ringdown spectroscopy (BA-CRDS) system for low temperature plasma diagnostics. The system can measure gas species in solutions, with a detection limit (minimum detectable absorbance) of 9.1 × 10 -5 , which is equivalent to a detection limit of 0.04 parts per billion for measuring OH radicals in water at 308 nm. With higher reflectivity ringdown mirrors and improved design of a Brewster angle cell, the detection limit can potentially be up to 10 -6 or lower. In this exploratory study, the absorption cross sections of HgBr 2 and H 2 O 2 in the aqueous phase at 256 nm are measured to be (1.8 ± 0.1) × 10 -18 cm 2 and (5.2 ± 0.5) × 10 -20 cm 2 , respectively. Furthermore, temporal profiles of absorbance from distilled water, HgBr 2 , and H 2 O 2 solutions when interacting with a helium atmospheric plasma jet are individually characterized at different plasma powers, gas flow rates, and/or solute concentrations. The observed linear temporal profiles of absorbance from the plasma-interacted water suggest formation of H 2 O 2 from plasma-generated OH radicals, while the nonlinear temporal profiles from the plasma-treated HgBr 2 solutions reveal possible removal of HgBr 2 by OH radicals. Our results demonstrate that the new BA-CRDS system is a powerful tool for quantification of reactive plasma species in multiphases or other complex settings.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Controlling the corrosion resistance of multi-principal element alloys

Multi-principal element alloys (MPEAs) offer the possibility of many degrees of freedom in the choice of alloying elements to produce either single phase solid solutions or more complex multiphase microstructures. Large ranges of material properties have been observed for MPEAs and mastery of the selection of elements and their compositions can enable novel combinations of properties not possible in traditional alloys. From the aqueous corrosion perspective, optimization of phase stability, control of heterogeneities, passive film identity and its protectiveness, as well as substrate properties such as metal-metal bond strength and activation energy associated with dissolution, can all be controlling factors governed by alloy composition and structure. These factors can mediate the electrochemical reactions controlling spontaneous corrosion. The quest for superior properties based on well-informed element choice is suggested as a path forward guiding MPEA formulations for corrosion performance. However, gaps in fundamental knowledge exist regarding (a) the specific functions of each element, (b) the behavior of elements in unusual combinations, and (c) the formation of complex protective oxides. These issues currently hold back progress in optimization of corrosion properties.

Scully, John R.↗

Ferrocene Bis(Sulfonate) Salt as Redoxmer for Fast and Steady Redox Flow Desalination

Desalination is considered a promising solution to alleviate water shortages, yet current methods are often restricted, due to challenges like high energy consumption, significant cost, or limited desalination capacity. In this study, we present a novel approach of redox flow desalination (RFD) utilizing the highly aqueous-soluble and reversible redox-active compound, potassium 1,1'-bis(sulfonate) ferrocene (1,1'-FcDS). This water-soluble organic compound yielded stable and rapid desalination, sustaining extended operation without notable decay and achieving an impressive desalination rate of up to 457.5 mmol·h -1 ·m -2 and energy consumption as low as 40.2 kJ·mol NaCl -1 . Specifically, the RFD device effectively desalinated a 50 mM NaCl solution to potable standards within 6000 s using 1,1'-FcDS. It maintained an average energy consumption of 178.16 kJ·mol NaCl -1 and exhibited negligible deterioration in desalination rate, energy efficiency, and charge efficiency throughout a rigorous 12,000 s cycling test. Furthermore, the versatility of this method was demonstrated by effectively treating saline water with varying initial concentrations from 10 mM to 50 mM, showcasing its potential across a broad spectrum of applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aqueous Alteration of Endeavour Crater Rim Apron Rocks

Mars Exploration Rover Opportunity is exploring Noachian age rocks of the rim of 22 km diameter Endeavour crater. Overlying the pre-impact lithologies and rim breccias is a thin apron of fine-grained sediments, the Grasberg fm, forming annuli on the lower slopes of rim segments. Hesperian Burns fm sandstones overly the Grasberg fm. Grasberg rocks have major element compositions that are distinct from Burns fm sandstones, especially when comparing interior compositions exposed by the Rock Abrasion Tool. Grasberg rocks are also different from Endeavour rim breccias, but have general compositional similarities to them. Grasberg sediments are plausibly fine-grained materials derived from the impact breccias. Veins of CaSO4 transect Grasberg fm rocks demonstrating post-formation aqueous alteration. Minor/trace elements show variations consistent with mobilization by aqueous fluids. Grasberg fm rocks have low Mn and high Fe/Mn ratios compared to the other lithologies. Manganese likely was mobilized and removed from the Grasberg host rock by redox reactions. We posit that Fe2+ from acidic solutions associated with formation of the Burns sulfate-rich sandstones acted as an electron donor to reduce more oxidized Mn to Mn2+. The Fe contents of Grasberg rocks are slightly higher than in other rocks suggesting precipitation of Fe phases in Grasberg materials. Pancam spectra show that Grasberg rocks have a higher fraction of ferric oxide minerals than other Endeavour rim rocks. Solutions transported Mn2+ into the Endeavour rim materials and oxidized and/or precipitated it in them. Grasberg has higher contents of the mobile elements K, Zn, Cl, and Br compared to the rim materials. Similar enrichments of mobile elements were measured by the Spirit APXS on West Spur and around Home Plate in Gusev crater. Enhancements in these elements are attributed to interactions of hydrothermal acidic fluids with the host rocks. Interactions of fluids with the Grasberg fm postdate the genesis of the Endeavour rim phyllosilicates. The aqueous alteration history of Endeavour rim rocks is complicated by different styles of alteration that have spanned the Noachian and Hesperian. Late stage acidic aqueous alteration of Grasberg fm materials is likely penecontemporaneous with the diagenesis of the sulfate-rich sediments of Meridiani Planum.

Mittlefehldt, David W.↗

Sequential Recovery of Critical Metals from Leached Liquor of Processed Spent Lithium-Ion Batteries

The processing and extraction of critical metals from black mass is important to battery recycling. Separation and recovery of critical metals (Co, Ni, Li, and Mn) from other metal impurities must yield purified metal salts, while avoiding substantial losses of critical metals. Solvent extraction in batch experiments were conducted using mixed metal sulphates obtained from the leach liquor obtained from spent and shredded lithium-ion batteries. Selective extraction of Mn 2+ , Fe 3+ , Al 3+ and Cu 2+ from simulated and real leached mixed metals solution was carried out using di-2-ethylhexylphophoric acid (D2EPHA) and Cyanex-272 at varying pH. Further experiments with the preferred extractant (D2EPHA) were performed under different conditions: changing the concentration of extractant, organic to aqueous ratio, and varying the diluents. At optimum conditions (40% v/v D2EPHA in kerosene, pH 2.5, O:A = 1:1, 25 °C, and 20 min), 85% Mn 2+ , 98% Al 3+ , 100% Fe 3+ , and 43% Cu 2+ were extracted with losses of only trace amounts (<5.0%) of Co 2+ , Ni 2+ , and Li + . The order of extraction efficiency for the diluents was found to be kerosene > Exxal-10 >>> dichloromethane (CH 2 Cl 2 ) > toluene. Four stages of stripping of metals loaded on D2EPHA were performed as co-extracted metal impurities were selectively stripped, and a purified MnSO 4 solution was produced. Spent extractant was regenerated after Fe 3+ and Al 3+ were completely stripped using 1.0 M oxalic acid (C 2 H 2 O 4 ).

25 ENERGY STORAGE↗

Using Al 3+ to Tailor Graphene Oxide Nanochannels: Impact on Membrane Stability and Permeability

Graphene oxide (GO) membranes, which form from the lamination of GO sheets, attract much attention due to their unique nanochannels. There is much interest in controlling the nanochannel structures and improving the aqueous stability of GO membranes so they can be effectively used in separation and filtration applications. This study employed a simple yet effective method of introducing trivalent aluminum cations to a GO sheet solution through the oxidation of aluminum foil, which modifies the nanochannels in the self-assembled GO membrane by increasing the inter-sheet distance while decreasing intra-sheet spacing. The Al 3+ modification resulted in an increase in membrane stability in water, methanol, ethanol, and propanol, yet decreased membrane permeability to water and propanol. These changes were attributed to strong interactions between Al 3+ and the membrane oxygenated functional groups, which resulted in an increase in membrane hydrophobicity and a decrease in the intra-sheet spacing as supported by surface tension, contact angle, atomic force microscopy, and X-ray photoelectron spectroscopy measurements. Our approach for forming Al 3+ modified GO membranes provides a method for improving the aqueous stability and tailoring the permeation selectivity of GO membranes, which have the potential to be implemented in vapor separation and fuel purification applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗