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At least 37 records · Page 2

Method to Estimate the Dissolved Air Content in Hydraulic Fluid

In order to verify the air content in hydraulic fluid, an instrument was needed to measure the dissolved air content before the fluid was loaded into the system. The instrument also needed to measure the dissolved air content in situ and in real time during the de-aeration process. The current methods used to measure the dissolved air content require the fluid to be drawn from the hydraulic system, and additional offline laboratory processing time is involved. During laboratory processing, there is a potential for contamination to occur, especially when subsaturated fluid is to be analyzed. A new method measures the amount of dissolved air in hydraulic fluid through the use of a dissolved oxygen meter. The device measures the dissolved air content through an in situ, real-time process that requires no additional offline laboratory processing time. The method utilizes an instrument that measures the partial pressure of oxygen in the hydraulic fluid. By using a standardized calculation procedure that relates the oxygen partial pressure to the volume of dissolved air in solution, the dissolved air content is estimated. The technique employs luminescent quenching technology to determine the partial pressure of oxygen in the hydraulic fluid. An estimated Henry s law coefficient for oxygen and nitrogen in hydraulic fluid is calculated using a standard method to estimate the solubility of gases in lubricants. The amount of dissolved oxygen in the hydraulic fluid is estimated using the Henry s solubility coefficient and the measured partial pressure of oxygen in solution. The amount of dissolved nitrogen that is in solution is estimated by assuming that the ratio of dissolved nitrogen to dissolved oxygen is equal to the ratio of the gas solubility of nitrogen to oxygen at atmospheric pressure and temperature. The technique was performed at atmospheric pressure and room temperature. The technique could be theoretically carried out at higher pressures and elevated temperatures.

Hauser, Daniel M.↗

Organic Evaporation and Oxidation Testing in Support of Hanford Sample-and-Send

The Hanford site has approximately 56 million gallons of radioactive mixed waste stored in 177 underground storage tanks. The Hanford Waste Treatment and Immobilization Plant (WTP) is being built to treat and immobilize the tank waste. The baseline method for immobilization of Low Activity Waste (LAW) through the WTP is vitrification, but additional immobilization capacity is needed to supplement the initial LAW melters. An alternative cementitious waste form is being investigated for that future immobilization method to supplement vitrification. However, one impediment to a cementitious waste form is the presence of Land Disposal Restricted (LDR) organic chemicals in tank waste. This work evaluates potential avenues to eliminate that impediment to permit possible use of a cementitious waste form and work towards a decision whether additional LDR organic pretreatment would be required. Savannah River National Laboratory (SRNL) performed testing using simulants to examine evaporation as a method to remove some prevalent organics from LAW. Spiking the caustic LAW simulant with selected regulated organic chemicals found one that clearly decomposes because of caustic instability. Oxidation testing of other organic chemicals found some LDR organics degrade as desired and others are stable in the presence of peroxide and permanganate. In addition to studies with simulants, a literature review was performed to evaluate radiological stability of LDR organics. Descriptions of the experimental details, equipment, and results are included in this report. Evaporation testing consisted of preparing the LAW simulant, spiking that simulant with organic chemicals, and evaporating the mixture via differential distillation. The apparatus was a laboratory-scale vacuum evaporator operated at 60 ±5 torr absolute (vacuum evaporation) and also at atmospheric pressure. The LAW simulant represented the liquid expected to be retrieved from the Hanford tank farms at approximately 4.0 M [Na + ] total sodium ion concentration. The concentration of the organic chemicals added was significantly higher than typically found in the tank waste samples since the higher levels were necessary to assist in analytical measurement and tracking of the spiked species. Organic chemicals were chosen for the work with a consideration of how their volatility compares with that of methanol. This was done by comparing the ratio of the pure water Henry’s law coefficient (K h ) of methanol to that of the compound in question (hereafter termed the K h ratio), where ratios above unity indicated less volatility than methanol. Methanol was chosen because it is a common regulated chemical with relatively low volatility but which has been removed by evaporation in previous laboratory work. While organic separation results depend on evaporator design, laboratory experiments verified that organic partitioning to the overhead condensate stream by evaporation is a practical process. The work reported here found difficulties in quantitative analysis of the organic chemicals in aqueous samples. Most of the time there was insufficient analysis to close a mass balance for evaporator runs, but qualitative evidence of carryover was obtained. The methods were also able to show whether organic chemicals were susceptible or resistant to solution oxidation in permanganate or hydrogen peroxide tests.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Self‐Consistent Model for Sorption and Transport in Polyimide‐Derived Carbon Molecular Sieve Gas Separation Membranes

Abstract Demand for energy‐efficient gas separations exists across many industrial processes, and membranes can aid in meeting this demand. Carbon molecular sieve (CMS) membranes show exceptional separation performance and scalable processing attributes attractive for important, similar‐sized gas pairs. Herein, we outline a mathematical and physical framework to understand these attributes. This framework shares features with dual‐mode transport theory for glassy polymers; however, physical connections to CMS model parameters differ from glassy polymer cases. We present evidence in CMS membranes for a large volume fraction of microporous domains characterized by Langmuir sorption in local equilibrium with a minority continuous phase described by Henry's law sorption. Using this framework, expressions are provided to relate measurable parameters for sorption and transport in CMS materials. We also outline a mechanism for formation of these environments and suggest future model refinements.

Sanyal, Oishi↗

Comparing and contrasting In-Vial and full-scale systems for sparging volatile analytes

Here, in-vial sparging was demonstrated as an effective, practical alternative to a full-scale sparging system for supporting the analysis of volatile constituents. Using elemental mercury (Hg 0 ) and toluene as representative purgeable analytes, the mass removal for various sparge configurations was measured and a reduced order model was developed and validated. In the primary experiments, Hg 0 in the sparge gas was trapped on activated carbon or gold, thermally desorbed, and quantified using atomic absorption or atomic fluorescence spectroscopy. Toluene experiments using the same in-vial sparge apparatus and sparge parameters were performed to demonstrate the applicability of the reduced order model to a broad range of compounds. Toluene removal was tracked by measuring the remaining toluene in sparged aliquots using Ultraviolet-visible (UV–Vis) spectroscopy. For the sparging, flow rates varied from 25 to 75 mL/min for periods from 0 to 30 min. Sparge performance, mass removal as a function of time, and sparge gas volume were measured for both in-vial and full-scale systems. A model based on dimensionless Henry's Law coefficient, normalized sparge gas volume, and fractional extent of equilibrium matched the experimental data for both compounds and provides a practical tool for future applications. For the conditions tested in this study, the calibrated model indicated that the sparge gas in the in-vial system reached approximately 33% of its equilibrium value before exiting the water surface, while a full-scale system reached approximately 100%. The tests validated the quality, reproducibility, and predictability of sparging performance for both full scale and in-vial sparge systems. Related factors such as waste generation, worker risk, and labor were also assessed. Full scale sparge systems provide the advantage of lower detection levels due to larger sample volume, while the in-vial sparge systems provide advantages for most other factors; including automatability, reducing secondary wastes, lessening the need to clean and check the sparge apparatus, and lowering labor and costs. The data and associated reduced order model support continued development and deployment of in-vial sparge platforms as a practical option for analysis of purgeable analytes such as volatile organic compounds and volatile metals/organometallics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solute- and solvent-based electromotive force cells for activity measurements of electroactive species in molten salts

A novel combination of solute- and solvent-based electrodes was used to determine the activities of NdCl 3 and GdCl 3 in molten LiCI-KCI eutectic using electromotive force measurements across a broad concentration range of dissolved electroactive species. First, an electrochemical cell using solute-based electrodes was used to define the relative activity of each species as a function of concentration and the concentration region in which Henry's law was applicable. Next, the electromotive force between a solute-based electrode with a known NdCl 3 or GdCl 3 concentration and a solvent-based electrode with a known electromotive force was measured. The solvent-based electrode potential was converted to the Lithium Eutectic Electrode (LEE) potential, which allowed the activity of dissolved NdCl 3 and GdCl 3 to be calculated at the concentrations measured using the solute-based electrodes. The described two-cell method uses electromotive force measurements to accurately determine the activity of electroactive species over a wide concentration range and provides a simple approach to closing the knowledge gap of thermochemical properties of molten salts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermochemical measurements of FeCl 2 in LiCl via electromotive force, coulometric titration, and cyclic voltammetry

The thermochemical properties of FeCl 2 in the LiCl-FeCl 2 binary system were determined at 913 K using electromotive force (emf) cells containing pre-made and coulometrically titrated molten salt compositions. Coulometric titration to in-situ change the salt composition utilizes the multiple valences of Fe ions and the tendency of Fe 3+ ions to comproportionate with Fe metal, forming additional Fe 2+ . The emf results were used to define the compositions in which Henry’s law is applicable, up to approximately 2 mol% FeCl 2 . Thermochemical quantities were determined from emf using a Standard Lithium Chloride Electrode (SLiCE) which defines 0 V as the reduction of Li + in pure LiCl at all temperatures. Validation of emf measurements was performed by comparing the formal potential measured by using cyclic voltammetry (2.224 ± 0.013 V vs SLiCE) and emf measurements (2.236 ± 0.004 V). In conclusion, this work shows that coulometric titration of an electroactive species that undergoes comproportionation can be used to rapidly obtain granular emf data in molten salt systems.

Coulometric titration↗

Noble gas adsorption to tuff

For this report a method was developed to measure trace noble gas element adsorption to the surfaces of geologic materials in the presence of a background gas that could potentially compete for surface adsorption sites. Adsorption of four noble gas elements (Ne, Ar, Kr, and Xe) at a concentration of 100 ppm in helium and nitrogen were measured on a sample of crushed tuff at 0, 15, 30, and 45°C. In addition, Ne, Ar, Kr, and Xe at 250 ppm and 500 ppm in nitrogen at 15°C were measured. Noble gas adsorption was found to increase with increasing atomic mass and decreasing temperature. It was also observed that the relative increase in noble gas element adsorption with decreasing temperature tends to increase with increasing atomic mass. Noble gas adsorption from nitrogen was approximately an order of magnitude greater than for the noble gases in helium. As the noble gas concentrations in nitrogen increased, adsorption increased in a slightly non-linear fashion which could be modeled using a Freundlich isotherm. For noble gas concentrations that were ≤100 ppm Henry's Law constant were calculated.

58 GEOSCIENCES↗

Coupled Interfacial and Bulk Kinetics Govern the Timescales of Multiphase Ozonolysis Reactions

Chemical transformations in aerosols impact the lifetime of particle phase species, the fate of atmospheric pollutants, and both climate- and health-relevant aerosol properties. Timescales for multiphase reactions of ozone in atmospheric aqueous phases are governed by coupled kinetic processes between the gas phase, the particle interface, and its bulk, which respond dynamically to reactive consumption of O 3 . However, models of atmospheric aerosol reactivity often do not account for the coupled nature of multiphase processes. Herein, to examine these dynamics, we use new and prior experimental observations of aqueous droplet reaction kinetics, including three systems with a range of surface affinities and ozonolysis rate coefficients ( trans -aconitic acid (C 6 H 6 O 6 ), maleic acid (C 4 H 4 O 4 ), and sodium nitrite (NaNO 2 )). Using literature rate coefficients and thermodynamic properties, we constrain a simple two-compartment stochastic kinetic model which resolves the interface from the particle bulk and represents O 3 partitioning, diffusion, and reaction as a coupled kinetic system. Our kinetic model accurately predicts decay kinetics across all three systems, demonstrating that both the thermodynamic properties of O 3 and the coupled kinetic and diffusion processes are key to making accurate predictions. An enhanced concentration of adsorbed O 3 , compared to gas and bulk phases is rapidly maintained and remains constant even as O 3 is consumed by reaction. Multiphase systems dynamically seek to achieve equilibrium in response to reactive O 3 loss, but this is hampered at solute concentrations relevant to aqueous aerosol by the rate of O 3 arrival in the bulk by diffusion. As a result, bulk-phase O 3 becomes depleted from its Henry's law solubility. This bulk-phase O 3 depletion limits reaction timescales for relatively slow-reacting organic solutes with low interfacial affinity (i.e., trans-aconitic and maleic acids, with k rxn ≈ 10 3 -10 4 M -1 s -1 ), which is in contrast to fast-reacting solutes with higher surface affinity (i.e., nitrite, with k rxn ≈ 10 5 M -1 s -1 ) where surface reactions strongly impact the observed decay kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrasound-Assisted Nonthermal, Nonequilibrium Separation of Organic Molecules from Their Binary Aqueous Solutions: Effect of Solute Properties on Separation

The separation of organic molecules in downstream processes, such as distillation, plays a vital role in biobased chemical production. A comprehensive study was performed here using ultrasonic energy to separate 11 organic molecules from their binary aqueous solutions under nonthermal, nonequilibrium, and phase-change free conditions. A batch sonoseparator with a three-stage mist collection unit allowed direct analysis of ultrasound-generated mist with an HPLC/GC and differentiation and quantification of the vapor and mist. The results showed that the alcohols (1-butanol, ethanol, 1-propanol, and methanol) and acetone were enriched in the ultrasound-generated mist with enrichment ratios of 3.2–5. On the other hand, ethylene glycol, glycerol, γ-valerolactone (GVL), glucose, and sucrose were diluted with dilution ratios in the range of 2.04–15.7 in the mist and vapor generated by ultrasound (or concentrated in the bulk solution). No enrichment nor dilution of acetic acid was observed. The role of various physicochemical parameters such as dynamic viscosity, surface tension, Henry’s law of solubility constant, vapor pressure, and octanol–water partition coefficient in the enrichment was examined. Furthermore, the hydrophobicity of the organic molecules represented by the octanol–water partition coefficient was found to play a crucial role in determining the separation characteristics of the molecules in ultrasound-generated mist and vapor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Imaging solvated oxygen atoms with a femtosecond laser

As a powerful oxidant, atomic oxygen (O) holds considerable promise for a variety of biomedical and industrial applications. However, the inability to quantify solvated oxygen atoms has prevented the determination of the fundamental parameters governing its behaviour in relevant aqueous environments. Here, we directly image ground-state oxygen atoms in water using femtosecond two-photon absorption laser-induced fluorescence. Measurements show that oxygen atoms persist for tens of microseconds in water, penetrating hundreds of micrometres into the liquid. This observed longevity has significant implications, suggesting a need to re-evaluate existing models of solvated atomic oxygen reactivity and transport. Beyond atomic oxygen, this technique is broadly applicable to other solvated atomic species of interest, including nitrogen (N) and hydrogen (H). This work establishes that radical atomic species can be quantified in liquid with ultrafast laser spectroscopy, providing the basis for the determination of key properties including reaction rates, chemical lifetimes, and Henry’s law constants.

Fluorescence spectroscopy↗

Formation of late-generation atmospheric compounds inhibited by rapid deposition

Reactive organic carbon species are important fuel for atmospheric chemical reactions, including the formation of secondary organic aerosol. However, in parallel to atmospheric oxidation processes, deposition can remove compounds from the atmosphere and impact downstream environments. To understand the impact of deposition on atmospheric oxidation, we present a framework for predicting and visualizing the fate of a molecule on the basis of the physicochemical properties of compounds (Henry’s law constant, vapour pressure and reaction rate constants), which are used to estimate timescales for oxidation and deposition. Further, by implementing our deposition rates in chemical models, we show that deposition substantially suppresses atmospheric reactivity and aerosol formation by removing early-generation products and preventing the formation of large fractions (up to 90%) of downstream, late-generation compounds. Deposition is frequently missing in the laboratory experiments and detailed chemical modelling, which probably biases our understanding of atmospheric composition.

54 ENVIRONMENTAL SCIENCES↗

Interaction energy and isosteric heat of adsorption between hydrogen and magnesium diboride

Hydrogen storage materials form a crucial research topic for future energy utilization employing hydrogen and among those of interest magnesium diboride (MgB 2 ) has shown its prevalence. In this study, a first-principles analytical adsorption model of one hydrogen molecule in the vicinity of various magnesium diboride crystal surfaces was developed in order to obtain surface thermodynamic properties as a function of molecular and lattice properties. Henry's law constant (K H ) and isosteric heat of adsorption (ΔH ads ) indicators of the affinity between a gaseous molecule and a solid surface are thus calculated. The results in this paper not only address questions pertaining to the first stage of hydrogen storage processes but also advance the understanding of physisorption thermodynamics of a neutral molecule (H 2 ) coming in contact with a layered metallic-like surface (MgB 2 ). Although the model is built from a framework of classical calculations, quantum effects are incorporated as the fractional charge of the ions on the free surfaces, which is essential for the calculation of analytic thermodynamic values that approximate calculations from other methods. To benchmark our theoretical models, periodic density functional calculations were performed to determine the interactions between H 2 and different MgB 2 surfaces from first-principles. By considering both the top and sublayers of MgB 2 in calculating interaction energy, we have analytically and computationally calculated the interaction energies of H 2 molecules and MgB 2 's terminated planes, and witnessed the strong dependence of interaction energies on surface charges. We have also observed a dipole flipping phenomenon which explains the discontinuity seen in the interaction energy graph of Mg(0001). Both analytical and computational results showed heat of adsorption at zero coverage varying at a very low range (<7 kJ mol -1 ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Methanediol from cloud-processed formaldehyde is only a minor source of atmospheric formic acid

Atmospheric formic acid is severely underpredicted by models. A recent study proposed that this discrepancy can be resolved by abundant formic acid production from the reaction ( 1 ) between hydroxyl radical and methanediol derived from in-cloud formaldehyde processing and provided a chamber-experiment-derived rate constant, k 1 = 7.5 × 10 −12 cm 3 s −1 . High-level accuracy coupled cluster calculations in combination with E,J -resolved two-dimensional master equation analyses yield k 1 = (2.4 ± 0.5) × 10 −12 cm 3 s −1 for relevant atmospheric conditions ( T = 260–310 K and P = 0–1 atm). We attribute this significant discrepancy to HCOOH formation from other molecules in the chamber experiments. More importantly, we show that reversible aqueous processes result indirectly in the equilibration on a 10 min. time scale of the gas-phase reaction HCHO + H 2 O ⇌ HOCH 2 OH (2) with a HOCH 2 OH to HCHO ratio of only ca . 2%. Although HOCH 2 OH outgassing upon cloud evaporation typically increases this ratio by a factor of 1.5–5, as determined by numerical simulations, its in-cloud reprocessing is shown using a global model to strongly limit the gas-phase sink and the resulting production of formic acid. Based on the combined findings in this work, we derive a range of 1.2–8.5 Tg/y for the global HCOOH production from cloud-derived HOCH 2 OH reacting with OH. The best estimate, 3.3 Tg/y, is about 30 times less than recently reported. The theoretical equilibrium constant K eq (2) determined in this work also allows us to estimate the Henry’s law constant of methanediol (8.1 × 10 5 M atm −1 at 280 K).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical-specific Parameters Dataset

The chemical-specific parameters dataset is searchable for physicochemical information for multiple chemicals simultaneously. After selecting chemicals of interest and the desired parameters, the RAIS will generate a table containing the values, chosen according to an established hierarchy. Results can be downloaded in Excel format. Over 40 parameters are available, including melting point, boiling point, density, density, vapor pressure, water solubility, and Henry’s Law constants. Thirteen primary sources are used to populate the dataset of chemical-specific parameters. These values should be used in cancer risk and noncancer hazard assessments for the calculation of preliminary remediation goals (PRGs), hazard characterization, and transport modeling. Users can select up to 1000 chemicals per query. The dataset supports environmental risk assessments, regulatory decision-making, and environmental planning with tools for benchmarking against risk-based standards. This structured approach ensures a robust evaluation of environmental risks tailored to regulatory needs.

Dolislager, Fred [Oak Ridge National Laboratory (O↗

SAM Code Enhancements for Fission Product Tracking of Noble Gases and Metals in MSRs

This report documents fiscal year 2026 enhancements to the System Analysis Module (SAM) for modeling fission product transport in liquid-fueled molten salt reactors (MSRs). The work advances three principal areas: noble gas transport, noble metal deposition, and user interface improvements. The noble gas transport capability integrates drift-flux gas transport, Henry’s law two-film interphase mass transfer with pressure-based nucleation suppression, Knudsen-regime pore diffusion into porous graphite with a conjugate salt-graphite interface constraint, built-in material properties, five Sherwood-number mass transfer correlations including three derived from high-fidelity NekRS simulations, and xenon-135 reactivity feedback through SAM’s point-kinetics model. This work also presents a comprehensive verification test suite, including new analytically verified cases for pressure-dependent onset of interphase gas transfer in a stagnant vertical pipe, a postulated FLiBe-graphite Xe extraction permeator, a gravity riser with a fission-product source, and a descending pipe with gas redissolution driven by hydrostatic pressure. A machine learning framework for bubble rise velocity prediction in molten salt systems is developed and benchmarked on molten-salt and diverse aqueous bubble datasets. The best-performing fine-tuned transfer-learning networks achieve an 82% reduction in RMSE relative to the Clift correlation, and is implemented directly in SAM. The noble metal transport capability is developed, including a liquid-wall deposition model and a gas-surface flotation mechanism that transfers insoluble particles entrained by sparging gas to wetted structures. Verification tests and demonstration cases cover the surface deposition, flotation efflux, and flotation shedding. Finally, a new [SpeciesTransport] input structure replaces positional global vectors with selfcontained, order-independent, named species blocks, simplifies the specification of multiphase species and decay chains, and remains fully compatible with existing SAM input files. Together, these developments improve the physical fidelity, verification basis, and usability of SAM for system-level analyses of fissionproduct behavior in MSRs.

Mui, Travis (ORCID:0000000303736470)↗

The effect of interfacial phenomena on gas solubility measurements in molten salts

The behavior of fission gases in molten fuel salt reactors governs activity transport from the reactor and can also affect the performance of the reactor itself. The gas solubility can be described thermodynamically by Henry’s law. However, the coupling of the condensed and gas phases depends on the interfacial area, which is difficult to measure or even to estimate. Surfaces of materials in the reactor will include disperse phases in the salt and porosity within the structural materials, covering a range of compositions and sizes. These attributes can affect measurements of fundamental properties such as gas solubility. Methods to obtain gas solubility, surface tension, interfacial energies, and bubble gas transport are reviewed. Recent data from manometric experiments are interpreted based on xenon sorption onto salt-wetted quartz.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Seawater Acidification and Bubble Plume Dispersion from Accidental Subsea CO 2 Pipeline Rupture: A Multiphase CFD Study

If a CO 2 reservoir or transmission pipeline were to leak, both the surrounding ecology and maritime traffic safety could be put at risk. To better understand and prepare for this risk, multiphase Computational Fluid Dynamics (CFD) models were built in ANSYS Fluent to capture the behavior of a leak once it enters the water. A 3D Eulerian–Eulerian model was used for validation, while a simplified 2D model was applied to simulate conditions at a 50-m depth. The models integrate bubble dynamics, gas holdup, CO 2 dissolution, dissolved species transport, and seawater acidification into a unified CFD framework. Mass transfer was calculated using the Hughmark correlation, and local seawater temperature and salinity were factored in to determine dissociation behavior and the relevant Henry’s Law constant. To confirm the 3D model’s accuracy, results were checked against two experimental datasets: the QICS field study and the Hauser Tank experiments. The team also modeled a hypothetical release scenario at the High Island 10L site and compared the results with earlier published work. The results show that at a depth of 50 m, the surrounding water column can completely absorb a CO 2 release at a rate of 35 kg/s, since the gas dissolves into the seawater as it rises toward the surface. Beyond confirming this mitigation capacity, the simulations shed light on how a leak would actually unfold in the environment, including the shape and movement of the rising bubble plume, how much CO 2 dissolves along the way, and the resulting shifts in seawater pH and pCO 2 . Together, this provides a practical framework for assessing how CO 2 leaks could affect marine environments in the Gulf of Mexico.

54 ENVIRONMENTAL SCIENCES↗