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At least 379 records · Page 21

Iodine Speciation Effects in LAW Feeds

Tests were conducted on a DM10 vitrification system with prototypical off-gas treatment system, which includes an SBS, WESP, and evaporator based on the design of the evaporator to be installed at the WTP for concentration of the liquid effluents. This allowed determination of the partitioning and speciation of iodine between the melter and the off gas system components, including liquid effluents from the SBS and WESP as well as in the evaporator condensate and concentrate. Evaporator testing was decoupled from melter testing to permit filtration and pH adjustments of process solutions prior to evaporation. In addition, a slip stream was pulled from the exhaust downstream of the WESP and High-Efficiency Particulate Air (HEPA) filters and passed through a caustic scrubber simulating the WTP caustic scrubber to assess iodine partitioning to the caustic scrubber liquid effluent. The tests were conducted using simulated Hanford LAW from tank AP-107, which is the planned first feed for Direct Feed LAW (DFLAW) operations, at a nominal feed concentration of 5.6 molar Na over about 120 hours of testing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Achieving high hydrogen productivities of 20 L/L-day via microbial electrolysis of corn stover fermentation products

Microbial electrolysis cells have the potential to generate renewable hydrogen from underused waste streams, however current devices have not reached very large productivity targets using real waste products at any scale. This study used a waste from fermented corn stover known as corn stover fermentation product to reach performance metrics that could be commercialized, if adequately scaled. Average current densities in MECs with mature biofilms reached 17.9 +/- 1.6 A/m 2 at an organic loading rate of 30 grams of chemical oxygen demand per liter of anode volume per day (g/L-day), reaching a maximum current density of 27.2 +/- 2.9 A/m 2 . Hydrogen productivities reached 20.2 +/- 2.0 L of H 2 per L anode volume per day (L/L-day). These represent the highest current densities and highest hydrogen productivities using a complex feedstock in a microbial electrolysis cell. Organic acids and sugars present in untreated substrate were converted at high percentages in MECs, with most above 90% conversion, at organic loading rates of 10, 20, and 30 g/L-day. The effect of periodic high liquid flow rates through the anode on performance was assessed. These tests, called pulsing, showed that hydrogen productivities and current densities increased most dramatically as flow was pulsed every hour at a baseline flow rate of 0.3 mL/min. These productivities show promise for high performance systems, if adequate scale up can be achieved.

09 BIOMASS FUELS↗

Trash Compaction and Processing System Trash Models and Evolved Gas Analysis of Trash Components

As part of the NASA Next Space Technologies for Exploration Partnerships (NextSTEP) Trash Compaction and Processing System (TCPS) program, the Generation 2 (Gen 2) Heat Melt Compactor (HMC) tests a variety of trash models (nominal, high liquid, and high cloth) in order to evaluate the technical risk associated with processing spacecraft trash. The trash components used in the trash models not only impacts the final solid trash disk quality, but also the water and gas effluent compositions. In order to better design an auxiliary system to treat the effluent streams, both the input trash components and the effluent must be characterized. Evolved gas analysis (EGA) methods are used to characterize the input trash components. The EGA results will be used to determine various HMC operational parameters, as well as to determine the optimal operation for the TCPS system.

Heat Melt Compactor↗

Sustainable extraction of rare earth elements from coal fly ash leachates using a recyclable ionic liquid

The growing demand for rare earth elements (REEs) has prompted interest in their recovery from alternative sources such as coal fly ash (CFA). This study explores the ionic liquid (IL) betainium bis(trifluoromethylsulfonyl)imide, [Hbet][Tf 2 N], for selective extraction of REEs from leachates of a Class C CFA. While previous studies have demonstrated the effectiveness of using [Hbet][Tf 2 N] to extract REEs from different types of CFA in direct ash-IL systems, this study investigates four CFA leachates prepared using HCl, HNO 3 , H 2 SO 4 , and citrate. Extraction experiments were conducted across varying pH levels and with additives such as ascorbic acid and betaine. Among the systems tested, [Hbet][Tf 2 N] achieved REE recoveries of 51% and 47% from the HCl and citrate leachates, respectively, comparable to 49% REE recovery in ash-IL extraction. Co-extraction of bulk elements was significantly reduced in the leachate-IL systems. Optimal REE extraction occurred near pH 11, and addition of ascorbic acid effectively suppressed iron co-extraction without compromising REE recovery. Recycling experiments demonstrated that [Hbet][Tf₂N] retains its performance over five cycles with manageable losses. These results reveal the promise of [Hbet][Tf 2 N] for effectively recovering REEs from leachates of solid wastes, highlighting its applicability as a sustainable strategy for other aqueous REE feedstocks.

chemistry↗

Post-Flight Microbial Analysis of Samples from the International Space Station Water Recovery System and Oxygen Generation System

The Regenerative, Environmental Control and Life Support System (ECLSS) on the International Space Station (ISS) includes the the Water Recovery System (WRS) and the Oxygen Generation System (OGS). The WRS consists of a Urine Processor Assembly (UPA) and Water Processor Assembly (WPA). This report describes microbial characterization of wastewater and surface samples collected from the WRS and OGS subsystems, returned to KSC, JSC, and MSFC on consecutive shuttle flights (STS-129 and STS-130) in 2009-10. STS-129 returned two filters that contained fluid samples from the WPA Waste Tank Orbital Recovery Unit (ORU), one from the waste tank and the other from the ISS humidity condensate. Direct count by microscopic enumeration revealed 8.38 x 104 cells per mL in the humidity condensate sample, but none of those cells were recoverable on solid agar media. In contrast, 3.32 x lOs cells per mL were measured from a surface swab of the WRS waste tank, including viable bacteria and fungi recovered after S12 days of incubation on solid agar media. Based on rDNA sequencing and phenotypic characterization, a fungus recovered from the filter was determined to be Lecythophora mutabilis. The bacterial isolate was identified by rDNA sequence data to be Methylobacterium radiotolerans. Additional UPA subsystem samples were returned on STS-130 for analysis. Both liquid and solid samples were collected from the Russian urine container (EDV), Distillation Assembly (DA) and Recycle Filter Tank Assembly (RFTA) for post-flight analysis. The bacterium Pseudomonas aeruginosa and fungus Chaetomium brasiliense were isolated from the EDV samples. No viable bacteria or fungi were recovered from RFTA brine samples (N= 6), but multiple samples (N = 11) from the DA and RFTA were found to contain fungal and bacterial cells. Many recovered cells have been identified to genus by rDNA sequencing and carbon source utilization profiling (BiOLOG Gen III). The presence of viable bacteria and fungi from WRS and OGS subsystems demonstrates the need for continued monitoring of ECLSS during future ISS operations and investigation of advanced antimicrobial controls.

Birmele, Michele N.↗

SRPPF Aqueous Recovery System Sorbent Testing

This study details preliminary testing of 7 inorganic sorbents for the solidification of the surrogate SRPPF aqueous recovery system liquid excess material of 4M sodium nitrate. Sorbents were subject to various mixing methods to incorporate sodium nitrate solution including static, rotating, and in situ paddle mixing. Paddle mixing was found to be the most effective mixing technique, while simple static tests were also successful, though only for some of the sorbents. Setting tests were performed to ensure that the sorbent sequestered the liquid without release through a conical paint filter. Recommended set times ranged from near immediate to 7 days. The set mixtures were investigated further using ultra-centrifugal liquid release testing, thermogravimetric analysis, and visual microscopy to understand the mechanism by which the sorbent sequestered the liquid. Most sorbents seem to incorporate liquid by sorbing it onto and into the sorbent particles, while Drierite ® , anhydrous calcium sulfate, created a crystal structure that bound the surrogate liquid. Overall, four sorbents are recommended for continued testing: Aquaset II, Aquaset IIG, Drierite ® , and Spill-X-A.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development of an Adsorption System for the Trash Compaction Processing System designed for operation in the International Space Station Express Rack

A water recovery system that utilizes adsorption to work with the Trash Compaction Processing System, formerly known as the Heat Melt Compactor, is being designed at NASA Ames Research Center as an option to current state of the art micro-gravity water management systems and contaminant control systems used in space. The adsorption system will be used in conjunction with the International Space Station Vacuum Exhaust system to avoid both the complexities of gas liquid phase separation in micro-gravity and venting of Trash Compaction Processing System effluents to the spacecraft cabin. The adsorption system will allow the water and gaseous effluents generated during the Trash Compaction System operation to be removed in a matter that meets the Vacuum Exhaust System venting rate requirements. The Trash Compaction Processing System is planned to fly as a Technology Demonstration on the International Space Station in the space station EXPRESS Rack facility. This paper describes the trade space that the adsorption system must operate in using the EXPRESS Rack facilities resources including the use of the Space Station Vacuum Exhaust System. Also described in this paper are design solutions to allow the adsorption system to function within the Express Rack and Vacuum Exhaust System Parameters.

Heat Melt Compactor↗

Cryogenic Carbon Capture™ (CCC) Status Report

The Cryogenic Carbon Capture™ (CCC) process separates CO2 from light gases in essentially any continuous process. CCC cools the gases to the frost or desublimation point of CO2 (-100 to -135 °C), separates and pressurizes the solids, and warms all streams to produce a CO2-depleted stream at ambient pressure and a pure (99+%) pressurized liquid CO2 stream typically to about 150 bar, both at ambient temperature. The process also recovers all gas moisture and most gas impurities less volatile than CO2 (NOx, SOx, Hg, PM, UHC, CCC, etc.) in separable streams. CCC nearly eliminates refrigeration energy for sensible temperature changes through heat integration. CCC does require energy to change the CO2 phase from a mixed vapor to a pressurized fluid, which represents the minimum energy required of any process for this separation. CCC uses additional energy for turbomachinery inefficiencies, heat losses, moisture removal and overall process pressure drop. Aside from these real-world energy demands, CCC operates near the minimum energy required to perform this gas separation by minimizing stream recycling. CCC compresses CO2 as a liquid, which is one of several reasons it costs about about half as much and consumes about half as much energy as an amine process when using flue gases with about 15% CO2. The process also has several major additional advantages, including (a) it is a bolt-on retrofit technology that does not need steam or any modification of existing equipment, (b) it recovers water and nearly all pollutants in addition to CO2 from the flue gas, (c) it enables highly efficient and cost effective energy storage at grid scale and on time scales of minutes, (d) it enables NG storage if the energy storage option is used, and (d) it has a small footprint and is minimally disruptive to existing plants, requiring only electrical power and a gas source to operate. Sustainable Energy Solutions (SES) has scaled this technology through several levels, the largest of which captures nominally 1 tonne of CO2/day and is called the skid system. Skid system field tests include utility-scale power plants, cement plants, heating plants, and other utility or industrial sites that burn natural gas, biomass, coal, shredded tires, municipal waste, and combinations of these fuels. These field tests produced 95-99% CO2 capture with CO2 purities of 99+% and initial CO2 contents that range from 4 to 28%. SES currently seeks to scale the system to merchant scale (10-80 tonnes of CO2 per day). In the process of doing so, SES has demonstrated the potential for CCC to contribute to energy storage and direct air capture in innovative and cost-effective ways. This presentation discusses the overall process and highlights results from field and in-house tests. These include (a) measured CO2 capture rates and operating conditions from in-house and field tests, and (b) predicted utility-scale costs and energy demands. This discussion also includes the application of the CCC technology to energy storage and direct air capture.

20 FOSSIL-FUELED POWER PLANTS↗

Recovery of Scandium from Bauxite Residue Using Sulfation Roasting-Assisted Water Leaching Process

Here, this study presents a method for recovering scandium from Indonesian bauxite residue (red mud) through a sulfation roasting-assisted water leaching process. Ammonium sulfate, (NH 4 ) 2 SO 4 , was chosen as the sulfate source for its lower melting point, less corrosivity, decreased toxicity, and the potential for ammonia recovery. A modified mixing system was introduced to improve the distribution of (NH 4 ) 2 SO 4 on red mud particles by combining them in water. A series of experiments were conducted to optimize the sulfation roasting process by examining the effects of the (NH 4 ) 2 SO 4 /red mud ratio, temperature, and roasting time. Subsequently, water leaching was optimized while considering the effect of leaching time and liquid-to-solid (L/S) ratio. The leaching of scandium from the roasted red mud showed rapid kinetics, even when using only water. Under the roasting conditions of 1/1 (g/g) (NH 4 ) 2 SO 4 /red mud ratio, 700°C, 60 min roasting time, and the leaching conditions of 65°C, 60 min, and 10 mL/g (L/S), over 90% of scandium was recovered, along with 64.4% Al leaching and below 8% Fe leaching. These results were further corroborated through comprehensive analyses such as x-ray diffraction (XRD) and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS). This study offers insights into an alternative, more environmentally friendly method for Sc recovery from red mud, promoting the sustainable use of hazardous waste like red mud.

ammonium sulfate↗

Integrated Bosch Process System Models for In-Situ Oxygen and Carbon Production

In-Situ Resource Utilization (ISRU) technology is a vital component to NASA’s mission of a sustainable presence on the Moon and Mars. Local resources can be leveraged to reduce resupply frequency and mass. Elements of the Bosch process, combined with the carbothermal reduction process, can produce oxygen on the lunar surface with minimal consumables. The Bosch process can also produce oxygen on the Martian surface by using the CO 2 -rich environment. Between both systems, adsorption pump, solar thermal energy, carbon formation reactor, and water recovery subsystems are modeled and integrated to create a functional model in MATLAB software. The model is used to simulate performance of the system and reduce mass, power, and volume requirements. This integrated system model provides a tool to scale ISRU technologies for oxygen and carbon production. The MATLAB model is created by developing a system of independent subsystem models that are solved for their quasi-steady state values which can be integrated with respect to time to determine the change in current states. A flexible time stepping method is used to ensure a high level of accuracy during periods of rapid change while still making use of a simple explicit integration method. The flexible time step is calculated for each independent subsystem and the minimum value from those is used as the overall time step. A flexible time step is calculated by dividing a resolution value, or the maximum change per time step, by the variables current rate of change. The maximum value from all points in space is used for subsystem models that contain multiple values. The process is done for every variable that is being monitored in each subsystem and the global minimum is used as that iteration’s timestep. Several assumptions used in the MATLAB model for fluid flow dynamics, such as 1-D gas flow through the sorption pump, are supported by modeling in Ansys Fluent software. The Lunar oxygen production system is outlined in Fig. 1. The carbothermal reduction subsystem uses solar energy to heat a mixture of lunar regolith and carbon powder to produce carbon monoxide. To begin, the carbon monoxide feeds to the modified Bosch subsystem along with hydrogen gas. The reactants then enter the carbon formation reactor where water and carbon powder are produced. Solar thermal energy is used to add energy to the reactor, but waste heat from the carbothermal process is another potential heat source. The water is collected and electrolyzed to produce hydrogen which reenters the Bosch subsystem, and the oxygen is stored for downstream use. The carbon powder is collected and feeds back into the carbothermal subsystem. The Martian oxygen production system uses the full Bosch process and is outlined in Fig 2. A CO 2 adsorption pump thermally cycles to scrub and pressurize CO 2 from the environment. Along with an initial supply of hydrogen, the reactants enter the Reverse Water Gas Shift Reactor (RWGSR) which produces carbon monoxide and water. Carbon monoxide and unreacted hydrogen enter the carbon formation reactor to produce water and carbon powder. The water is collected from both reactors and electrolyzed to reintroduce hydrogen and store oxygen for propellant production or life support. Carbon is removed from the carbon formation reactor and stored. The adsorption pump utilizes rapid cycle temperature swings within a stack of zeolite coated surfaces. The subsystem model solves 1-D quasi-steady conservation laws of the quasi-steady form, shown in Eq. 1, for the gas stream and heat exchange liquid to predict performance parameters such as breakthrough capacity and optimum cycle time. The source term S is used to capture interactions between the fluid flows and the sorbent. A quasi-steady-state scheme is used where no time derivatives appear in the governing equations, except for those in the source terms. This results in an autonomous system, where ∂F/∂x = ƒ(F). The fluxes F are provided at the inlet, and an explicit method is used to solve for the spatial distribution of F. The heat and mass flows to the sorbent are then extracted from the source terms. These flows are numerically integrated to produce a 1-D solution for the system’s state as a function of both time and space. The body of the adsorption pump is separated into two semi-independent models: the heat exchanger fluid flow and gas flow through the zeolite coated surfaces. Both models are solved using the above-described method to find a 1-D solution as a function of space and interact only once a timestep is taken. The interaction point is the sorbent through which all heat transfer between the two models must occur. Sorbent mass adsorption is calculated using the Lagergren model, shown in Eq. 2, where the transfer coefficient, λ D , is found by solving a system of nondimensionalized equations derived by using the heat and mass transfer analogy for transport phenomena. Using Grade 544 Type 13X zeolite as the sorbent material, the equilibrium concentration, θ eq , is calculated using the k-site Langmuir isotherm and fit parameters. Additionally, the enthalpy of adsorption used in the model is computed by interpolation of available data [1]. The subsystem model was validated using the Rapid Cycle Temperature Swing Adsorption (RC-TSA) pump. The solar thermal energy subsystem focuses on a solar concentrator concept with a heat exchanger to heat the reactants before entering the carbon formation reactor. The subsystem model assumes a fixed solar flux and reflector efficiency to calculate the reactant temperature given the incoming temperature, pressure, and exchanger geometry. The receiver is a custom manufactured series of copper blocks with serpentine channels to increase its surface area and the residence time of the reactants to heat up to 550 °C. The subsystem model was validated using a heat exchanger developed at NASA Glenn Research Center (GRC). The solar thermal energy subsystem focuses on a solar concentrator concept with a heat exchanger to heat the reactants before entering the carbon formation reactor. The subsystem model assumes a fixed solar flux and reflector efficiency to calculate the reactant temperature given the incoming temperature, pressure, and exchanger geometry. The receiver is a custom manufactured series of copper blocks with serpentine channels to increase its surface area and the residence time of the reactants to heat up to 550 °C. The subsystem model was validated using a heat exchanger developed at NASA Glenn Research Center (GRC).

In situ Resource Utilization↗

A Simple and Flexible Infusion Platform for Automated Native Mass Spectrometry Analysis

High throughput native mass spectrometry analysis of proteins and protein complexes has been enabled by recent development of infusion and liquid chromatography (LC) systems, which often include complete LC pumps without fully utilizing their gradient flows. We demonstrated a lower-cost infusion cart for native mass spectrometry applications using a single isocratic solvent pump that can operate at both nano- and high-flow configurations (0.05-150 $μ$L/min) for both infusion and online buffer exchange experiments. In conclusion, the platform is controlled via open-source software and can potentially be expanded for customized experimental designs, offering a lower cost alternative to laboratories with limited budgets and/or needs in student training.

47 OTHER INSTRUMENTATION↗

Application of Ionic Liquids for the Recycling and Recovery of Technologically Critical and Valuable Metals

Population growth has led to an increased demand for raw minerals and energy resources; however, their supply cannot easily be provided in the same proportions. Modern technologies contain materials that are becoming more finely intermixed because of the broadening palette of elements used, and this outcome creates certain limitations for recycling. The recovery and separation of individual elements, critical materials and valuable metals from complex systems requires complex energy-consuming solutions with many hazardous chemicals used. Significant pressure is brought to bear on the improvement of separation and recycling approaches by the need to balance sustainability, efficiency, and environmental impacts. Due to the increase in environmental consciousness in chemical research and industry, the challenge for a sustainable environment calls for clean procedures that avoid the use of harmful organic solvents. Ionic liquids, also known as molten salts and future solvents, are endowed with unique features that have already had a promising impact on cutting-edge science and technologies. This review aims to address the current challenges associated with the energy-efficient design, recovery, recycling, and separation of valuable metals employing ionic liquids.

36 MATERIALS SCIENCE↗

Space Station Freedom combustion research

Extended operations in microgravity, on board spacecraft like Space Station Freedom, provide both unusual opportunities and unusual challenges for combustion science. On the one hand, eliminating the intrusion of buoyancy provides a valuable new perspective for fundamental studies of combustion phenomena. On the other hand, however, the absence of buoyancy creates new hazards of fires and explosions that must be understood to assure safe manned space activities. These considerations - and the relevance of combustion science to problems of pollutants, energy utilization, waste incineration, power and propulsion systems, and fire and explosion hazards, among others - provide strong motivation for microgravity combustion research. The intrusion of buoyancy is a greater impediment to fundamental combustion studies than to most other areas of science. Combustion intrinsically heats gases with the resulting buoyant motion at normal gravity either preventing or vastly complicating measurements. Perversely, this limitation is most evident for fundamental laboratory experiments; few practical combustion phenomena are significantly affected by buoyancy. Thus, we have never observed the most fundamental combustion phenomena - laminar premixed and diffusion flames, heterogeneous flames of particles and surfaces, low-speed turbulent flames, etc. - without substantial buoyant disturbances. This precludes rational merging of theory, where buoyancy is of little interest, and experiments, that always are contaminated by buoyancy, which is the traditional path for developing most areas of science. The current microgravity combustion program seeks to rectify this deficiency using both ground-based and space-based facilities, with experiments involving space-based facilities including: laminar premixed flames, soot processes in laminar jet diffusion flames, structure of laminar and turbulent jet diffusion flames, solid surface combustion, one-dimensional smoldering, ignition and flame spread of liquids, drop combustion, and quenching of panicle-air flames. Unfortunately, the same features that make microgravity attractive for fundamental combustion experiments, introduce new fire and explosion hazards that have no counterpart on earth. For example, microgravity can cause broader flammability limits, novel regimes of flame spread, enhanced effects of flame radiation, slower fire detector response, and enhanced combustion upon injecting fire extinguishing agents, among others. On the other hand, spacecraft provide an opportunity to use 'fire-safe' atmospheres due to their controlled environment. Investigation of these problems is just beginning, with specific fire safety experiments supplementing the space based fundamental experiments listed earlier; thus, much remains to be done to develop an adequate technology base for fire and explosion safety considerations for spacecraft.

Faeth, G. M.↗

Process-structure-property relationships for droplet-on-demand liquid-metal-jetted parts

Liquid metal jetting droplet-on-demand additive manufacturing is an attractive alternative to industry-standard, laser-based metal additive manufacturing techniques that use powder feedstocks and produce large heat affected zones. Liquid metal jetting provides a low feedstock footprint, minimal materials waste, less contamination and inclusions from feedstock, and is compatible with a large range of materials. However, little has been reported on the liquid metal jetting process-structure-property relationships that are crucial to understanding how to consistently print high quality metal parts. We investigate the effects of build plate temperature, infill pattern, and track raster rate on the macro- and microstructure, density, hardness, and tensile strength of metal parts created with our custom droplet-on-demand setup using pure tin feedstock as a surrogate for more relevant structural materials. We found that although the build plate temperature had the largest influence on the structure and properties, the infill pattern is an important factor for optimal structural integrity. It was observed that the track raster rate influenced track-to-track porosity and should be considered in toolpath development. Despite printing in ambient air, we could not identify oxide on the surface or in the bulk of the parts and saw no adverse effects on microstructure or tensile performance. The results and methods of this study will help guide future work in optimizing the liquid metal jetting process to reliably print parts using any liquid metal jetting system for a wide variety of metal feedstocks.

36 MATERIALS SCIENCE↗

Dissolution of Fluoride Salts in Hanford Tank Waste

The Direct Feed High-Level Waste (DFHLW) strategy seeks to bypass the Hanford Waste Treatment and Immobilization Plant Pretreatment Facility while retaining some processing functions to maximize waste feed loading and minimize high-level waste (HLW) waste volume. The DFHLW flowsheet needs leaching, washing, and solids concentration operations either in new or existing tanks. The effectiveness and efficiency of sludge washing has a substantial impact on DST space, mission duration, and the evaporation and low-activity waste (LAW) treatment operations required by these large wash-water additions. One target species requiring washing is fluoride. The HLW glass composition limits for fluorine drive operations to dissolve fluoride-bearing salts into the LAW fraction and thereby maximize waste loading in HLW glass. The fluoride in many high-level wastes at Hanford is predominantly in the form of fluoride-salt precipitates: villiaumite (NaF), kogarkoite (Na 3 FSO 4 ), and natrophosphate (Na 7 F(PO 4 ) 2 ·19H 2 O). Fluoride produces melter off-gas that creates corrosion risk in the off-gas system piping, while the sulfate and phosphate in the fluoride double salts kogarkoite and natrophosphate can be detrimental to glass waste loading. Fluoride salts are sparingly soluble, with solubilities ranging from approximately 40 to 130 kg per kL of pure water, and the dissolution kinetics of the three fluoride salts are not well known. Unexpected delays in a tank dissolution process could be encountered as a result of the lack of information about dissolution rates. In addition, if the double salts show transient non-stoichiometric dissolution of fluoride versus phosphate or sulfate, unexpectedly high concentrations of one of these other constituents could be produced. Washington River Protection Solutions authorized Pacific Northwest National Laboratory to collect the available data for fluoride salt dissolution rate, provide a scoping estimate of dissolution time if possible, and identify gaps in the understanding and predictive capability for estimating dissolution time. Open literature and Hanford reports were reviewed to document, understand, and (where possible) evaluate limitations on fluoride salt equilibria and dissolution kinetics, including both mass transport and surface reaction rate. Scoping estimates of dissolution time were made for mass-transfer-controlled dissolution of spherical particles of fluoride salts suspended in liquid. This is not the only potential governing mechanism; dissolution could be substantially slower if the surface reaction rate (the rate of release of ions from the surface) is the controlling mechanism. When the minimum amount of water for complete dissolution is used and the slip velocity between the liquid and suspended particles is less than or equal to the terminal settling velocity, the estimated mass-transfer rates allow 0.1 mm particles of fluoride salt to dissolve in minutes at 25 °C in water containing no other dissolved salts. Much larger solids, such as the 6-mm chunks that have been seen in heels, could take a few hours to more than a week to dissolve. The actual dissolution times will depend strongly on the actual slip velocity, the extent of particle suspension, constraint by surface reaction rates, the ratio of solvent to solid, and the presence of common ions that shift the solubility equilibria to restrict dissolution of fluoride salts.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Polyethylene Upcycling to Liquid Alkanes in Molten Salts under Neat and External Hydrogen Source-Free Conditions

Development of facile approaches to convert plastic waste into liquid fuels under neat conditions is highly desired but challenging, particularly without noble metal catalysts and an external hydrogen source. Herein, highly efficient and selective polyethylene-to-gasoline oil (branched C 6 –C 12 alkanes) conversion was achieved under mild conditions (<170 °C) using commercially available AlCl 3 -containing molten salts as reaction media and to provide catalytic sites (no extra solvents, additives, or hydrogen feeding). The high catalytic efficiency and selectivity was ensured by the abundant active Al sites with strong Lewis acidity (comparable to the Al type in acidic zeolite) and highly ionic nature of the molten salts to stabilize the carbenium intermediates. Dynamic genesis of the Al sites was elucidated via time-resolved Al K-edge soft X-ray and 27 Al NMR, confirming the tricoordinated Al 3+ as active sites and its coordination with the as-generated alkene/aromatic intermediates. Further, the carbenium formation and polyethylene chain variation was illustrated by inelastic neutron scattering (INS) and an isotope-labeling experiment. Theoretical simulations further demonstrated the successive hydride abstraction, β-scission, isomerization, and internal hydrogen transfer reaction pathway with AlCl 3 as active sites. This facile catalytic system can further achieve the conversion of robust, densely assembled, and high molecular weight plastic model compounds to liquid alkane products in the diesel range.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Counterflow Regolith Heat Exchanger

A problem exists in reducing the total heating power required to extract oxygen from lunar regolith. All such processes require heating a great deal of soil, and the heat energy is wasted if it cannot be recycled from processed material back into new material. The counterflow regolith heat exchanger (CoRHE) is a device that transfers heat from hot regolith to cold regolith. The CoRHE is essentially a tube-in-tube heat exchanger with internal and external augers attached to the inner rotating tube to move the regolith. Hot regolith in the outer tube is moved in one direction by a right-hand - ed auger, and the cool regolith in the inner tube is moved in the opposite direction by a left-handed auger attached to the inside of the rotating tube. In this counterflow arrangement, a large fraction of the heat from the expended regolith is transferred to the new regolith. The spent regolith leaves the heat exchanger close to the temperature of the cold new regolith, and the new regolith is pre-heated close to the initial temperature of the spent regolith. Using the CoRHE can reduce the heating requirement of a lunar ISRU system by 80%, reducing the total power consumption by a factor of two. The unique feature of this system is that it allows for counterflow heat exchange to occur between solids, instead of liquids or gases, as is commonly done. In addition, in variants of this concept, the hydrogen reduction can be made to occur within the counterflow heat exchanger itself, enabling a simplified lunar ISRU (in situ resource utilization) system with excellent energy economy and continuous nonbatch mode operation.

Zubrin, Robert↗

Unraveling Anion-Specific Inhibition and Structural Modulation of Gibbsite Crystallization: Implications for Aluminum Mobility in Natural and Engineered Systems

Gibbsite (α-Al(OH) 3 , sometimes designated as γ-Al(OH) 3 ) plays a crucial role in the chemistry of aluminum in the environment and industry, yet its crystallization behavior under multianionic conditions is not well understood. Here, in this study, we investigate how six common anions─fluoride (F – ), chloride (Cl – ), bromide (Br – ), nitrate (NO 3 – ), sulfate (SO 4 2– ), and phosphate (PO 4 3– )─influence the mineralization, structure, and morphology of gibbsite at room temperature. The results show that PO 4 3– , SO 4 2– , and F – strongly inhibit gibbsite formation, stabilizing amorphous or alternative crystalline phases such as nordstrandite and cryolite. On the contrary, Cl – , Br – , and NO 3 – allow partial to complete crystallization of gibbsite without significant morphological changes. Solid-state 27 Al magic angle spinning nuclear magnetic resonance provides crucial insight into aluminum coordination environments in both crystalline and amorphous phases, distinguishing between octahedral, pentahedral, and tetrahedral Al species. The density functional theory calculations reveal a direct correlation between the Al–X bond strength and the inhibition of crystallization, following the order: PO 4 3– > SO 4 2– > F – > NO 3 – > Cl – > Br – . These findings offer molecular-scale insights into anion-specific effects on aluminum hydroxide nucleation and transformation, improving the understanding of gibbsite formation and aluminum cycling in soils, phosphate retention, contaminant immobilization, and waste treatment strategies in nuclear and industrial settings. These insights can also guide the controlled synthesis of aluminum hydroxide materials with tailored crystallinity and morphology via liquid-assisted methods.

Anions effect↗