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Geochemical characterization of lithium deposition in fossil energy wastes

Lithium is a critical mineral used in rechargeable batteries for electric vehicles (EVs) and future modernization of electric grids with sensitive supply chains that are subject to volatility. Therefore, methods to recover lithium from domestic unconventional sources are actively being pursued in the United States. Herein, we report on the lithium recovery potential from four fossil energy waste feedstocks: oil and gas drill cuttings (sample number n = 16); oil and gas produced waters (n > 200) from Marcellus, Bakken and Permian basins; coal byproducts (n>20), such as coal ash; and acid mine drainage treatment solids (AMD solids). Select solid samples underwent sequential extraction to explore lithium hosting phases and simple organic and inorganic acid extraction to explore lithium recovery potential. Our preliminary results found lithium concentrations up to 440 mg/kg in select AMD treatment solids and up to 300 mg/L in Marcellus Shale produced waters, demonstrating these sources have lithium yield potentials comparable to conventionally mined lithium ores and brines. Sequential extractions revealed that lithium is mostly associated with clay and silicate phases in shale drill cuttings, whereas lithium resides in Fe,Mn-oxide reducible phases in AMD solids. Further, the lithium content in produced waters has a strong linear relationship with total dissolved solid (TDS) levels in three separate oil and gas basins. At the same TDS level, Marcellus Shale produced waters contain more lithium compared to Bakken Shale and Permian Basin waters, with higher percentages of Ca and Mg, major cations that might impact lithium recovery efficiencies. Our study demonstrates the heterogeneity of lithium hosts from different fossil energy wastes. Characterization results will inform future lithium recovery from these different feedstocks.

Stuckman, Mengling↗

Williston Basin Resource Study for Commercial-Scale Subsurface Hydrogen Storage

The Energy & Environmental Research Center (EERC), in partnership with the U.S. Department of Energy (DOE) National Energy Technology Laboratory (NETL), the EERC’s State Energy Research Center (SERC), MPLX Operations LLC, and TC Energy Development Holdings Inc. (a subsidiary of TC Energy Corporation), studied the potential for subsurface hydrogen storage and recovery in the Williston Basin of western North Dakota. The project’s goal was to evaluate the feasibility of large-scale, secure geologic H 2 storage to support future hydrogen generation, storage, and use. This work included laboratory testing, H 2 –rock–fluid exposure experiments, literature reviews on H 2 embrittlement, and reservoir modeling and simulations. The study included an assessment of storage potential across three types of storage reservoirs using both reservoir simulation and DOE’s web-based tool SHASTA-HELP (Subsurface Hydrogen Assessment, Storage, and Technology Acceleration – Hydrogen Estimator for Logistical Planning), as well as investigation of potential H 2 production and markets for commercial-scale deployment. Building on prior EERC gas storage research, three storage options were selected for detailed evaluation: the Broom Creek Formation (a clastic saline reservoir), the Dickinson Lodgepole Mounds (DLM) complex (carbonate mud mound structures) of the Lodgepole Formation (an active oil and gas producing reservoir), and the Dunham Salt Interval of the Piper Formation (to be used for engineered salt cavern development). These targets were prioritized based on prior EERC research using datasets related to seal capacity, reservoir quality, mechanical integrity, and injectivity. Exposure tests on Broom Creek and DLM samples showed mineral dissolution and precipitation that increased brine salinity and altered reservoir rock surfaces. Although these results provide useful insight, they are limited by small sample sizes and short-term (30-day) exposure, requiring further study to assess long-term storage integrity. Salt formations were not tested because of their known nonreactivity and established mechanical stability. Results of reservoir simulations performed for a single site demonstrated that the Broom Creek Formation may be capable of receiving up to 42,000 tonnes of injected H 2 over 7 months via one well. H 2 recovery took place over 5 months, resulting in approximately 26,000 tonnes (~62% without cushion gas [CG]). This work suggests water production may be important and subsequent cycles of injection and production may perform more efficiently; however, significant site-specific work in the future is needed to assess actual reservoir performance of injection and withdrawal of H 2 storage. For oil reservoir potential, a multiple-well model was used to simulate injection of approximately 32,000 tonnes of H 2 into a single wellbore while simultaneously producing in place reservoir fluids from four offset wells to maintain reservoir pressure. The simulation results suggested a high recovery (~98%); in addition, cost advantages through existing infrastructure could be realized. Challenges in this reservoir include vi managing gas purity and leakage risks. In both scenarios, production of H 2 takes place in a single-well scenario with 10 cycles (7 months of injection and 5 months of production) over 10 years. Finally, the use of engineered caverns in the Dunhan Salt was evaluated, and the results suggest that while they have a smaller capacity (<1000 tonnes per cavern), they exhibit nearly complete gas recovery (>99%), fast response times, and low purity risk. While caverns in North Dakota may be smaller in capacity, fields can be developed in galleries to accommodate the volumetric needs and rapid turnaround times necessary to meet market demands. Geographic limitations and thin salt intervals in North Dakota may represent less total storage potential than salt domes elsewhere, but significant opportunities exist to expand this market for gas storage in North Dakota. A basinwide assessment was performed to estimate a first-of-its-kind value for H 2 storage on a large scale. DOE’s SHASTA-HELP, combined with EERC simulation work, was used to perform the assessment. Estimated H 2 storage potential varied widely for each formation type. The Broom Creek saline formation was estimated to have a storage potential of approximately 1.7–90.5 million tonnes (MMt). The DLM oil reservoirs were estimated to have 0.07–0.19 MMt of capacity. Notably, each of these estimates relies on significant assumptions regarding reservoir thickness, porosity, permeability, and CG needed for operation. Much research is needed to understand the true site-specific storage resource potential of each formation. Using the Dunham Salt Interval for cavern development may result in as much as 4.79 MMt (up to 2.87 MMt working gas) of H 2 storage potential. An important note for consideration is that the values presented here need significantly more geological characterization and engineering assessments prior to gaining confidence in performance. This will be a focal point for future research and development needs. The basinwide evaluation also indicated that North Dakota has significant H 2 generation potential, with estimates up to a possible 13 MMt annually, suggesting a substantial opportunity for H 2 market development and thus the need for commercial-scale H 2 storage to facilitate growth and resilience. Key Recommendations 1. Conduct detailed site characterization (3D seismic, well logs, core sampling) to reduce geologic uncertainty. 2. Perform techno-economic analyses incorporating market, regulatory, and incentive frameworks. 3. Investigate long-term interactions among H 2 , CGs, well materials, and formations to assess risks. 4. Develop pilot- and field-scale demonstrations to validate models and establish best practices.

03 NATURAL GAS↗

Cellulose Nanofibers as Rheological Modifiers to Improve Biomass Slurry Processing and Fermentation

This study investigates the enhancement of biomass slurry processability through the addition of rheological modifiers, focusing on carboxymethyl cellulose (CMC) and TEMPO-mediated oxidized cellulose nanofibrils (TCNF). Three sets of experiments were conducted to assess the effects of these additives on slurry processing and fermentation. Initial experiments evaluated the slurry extrudability, concluding that TCNF aids extrusion similarly to CMC. Subsequent experiments explored slurry viscosity reduction mechanisms, revealing that while CMC significantly reduced the viscosity, TCNF’s impact is negligible. Additionally, TCNF performed comparably to CMC in water retention tests across different conditions, which suggests that TCNF have potential as an effective additive for maintaining slurry fluidity at high solid concentrations through enhanced water retention. Lastly, both additives were investigated to ensure that they did not impact hydrolyzed biomass fermentation. The findings suggest that TCNF’s mechanisms differ from those of traditional water-soluble polymers like CMC, offering insights into novel approaches to improve the biomass processing efficiency and subsequent fermentation.

Jamieson, Zachary↗

Effect of geometry on airfoil icing characteristics

A droplet trajectory computer code is used to predict the water droplet impingement characteristics of several low- and medium-speed airfoils. The maximum impingement efficiency, total collection efficiency, and limits of impingement are analyzed as functions of the airfoil geometry and freestream conditions. The airfoil geometry is represented by leading edge radius, maximum thickness, maximum camber, and angle of attack. The analysis shows that the primary effects are an increase in maximum impingement efficiency with a decrease in leading edge radius, a reduction in total collection efficiency for thicker airfoils, and a change in the limits of impingement for airfoils of different maximum camber.

Bragg, M. B.↗

Microwave remote sensing of soil moisture

Knowledge of soil moisture is important to many disciplines, such as agriculture, hydrology, and meteorology. Soil moisture distribution of vast regions can be measured efficiently only with remote sensing techniques from airborne or satellite platforms. At low microwave frequencies, water has a much larger dielectric constant than dry soil. This difference manifests itself in surface emissivity (or reflectivity) change between dry and wet soils, and can be measured by a microwave radiometer or radar. The Microwave Sensors and Data Communications Branch is developing microwave remote sensing techniques using both radar and radiometry, but primarily with microwave radiometry. The efforts in these areas range from developing algorithms for data interpretation to conducting feasibility studies for space systems, with a primary goal of developing a microwave radiometer for soil moisture measurement from satellites, such as EOS or the Space Station. These efforts are listed.

Shiue, J. C.↗

Waste water processing technology for Space Station Freedom - Comparative test data analysis

Comparative tests were conducted to choose the optimum technology for waste water processing on SSF. A thermoelectric integrated membrane evaporation (TIMES) subsystem and a vapor compression distillation subsystem (VCD) were built and tested to compare urine processing capability. Water quality, performance, and specific energy were compared for conceptual designs intended to function as part of the water recovery and management system of SSF. The VCD is considered the most mature and efficient technology and was selected to replace the TIMES as the baseline urine processor for SSF.

Miernik, Janie H.↗

Microwave Processing of Planetary Surfaces for the Extraction of Volatiles

In-Situ Resource Utilization will be necessary for sustained exploration of space. Volatiles are present in planetary soils, but water by far has the most potential for effective utilization. The presence of water at the lunar poles, Mars, and possibly on Phobos opens the possibility of producing LOX for propellant. Water is also a useful radiation shielding material , and valuable to replenish expendables (water and oxygen) required for habitation in space. Because of the strong function of water vapor pressure with temperature, heating soil effectively liberates water vapor by sublimation. Microwave energy will penetrate soil and heat from within much more efficiently than heating from the surface with radiant heat. This is especially true under vacuum conditions since the heat transfer rate is very low. The depth of microwave penetration is a strong function of the microwave frequency and to a lesser extent on soil dielectric properties. Methods for complex electric permittivity and magnetic permeability measurement are being developed and used for measurements of lunar soil simulants. A new method for delivery of microwaves deep into a planetary surface is being prototyped with laboratory experiments and modeled with COMSOL MultiPhysics. We are planning to set up a planetary testbed in a large vacuum chamber in the coming year. Recent results are discussed.

Ethridge, Edwin C.↗

Microwave Processing of Planetary Surfaces for Volatile Extraction

In-Situ Resource Utilization will be necessary for sustained exploration of space. Volatiles are present in planetary soils, but water by far has the strongest potential for effective utilization. The presence of water at the lunar poles, Mars, and possibly on Phobos opens the possibility of producing LOX for propellant. Water is also a useful radiation shielding material and water (and oxygen) are expendables that are also required for habitation in space. Because of the strong function of water vapor pressure with temperature, heating soil effectively liberates water vapor by sublimation. Microwave energy will penetrate soil and heat from within much more efficiently than heating from the surface with radiant heat. This is especially true under vacuum conditions since the heat transfer rate is very low. The depth of microwave penetration is a strong function of the microwave frequency and to a lesser extent on soil dielectric properties. Methods for measuring the complex electric permittivity and magnetic permeability are being developed and have been measured for some lunar soil simulants at 0.5, 2.45, and 10 GHz from room temperature down to liquid nitrogen temperature. A new method for delivery of microwaves deep into a planetary surface is being prototyped with laboratory experiments and modeled with COMSOL MultiPhysics. We have plans to set up a planetary testbed in a large vacuum chamber in the coming year. Recent results will be presented.

Ethridge, Edwin C.↗

Finite Element Analysis of Three Methods for Microwave Heating of Planetary Surfaces

In-Situ Resource Utilization will be Ground Breaking technology for sustained exploration of space. Volatiles are present in planetary regolith, but water by far has the most potential for effective utilization. The presence of water at the lunar poles and Mars opens the possibility of using the hydrogen for propellant on missions beyond Earth orbit. Likewise, the oxygen could be used for in-space propulsion for lunar ascent/descent and for space tugs from low lunar orbit to low Earth orbit. Water is also an effective radiation shielding material as well as a valuable expendable (water and oxygen) required for habitation in space. Because of the strong function of water vapor pressure with temperature, heating regolith effectively liberates water vapor by sublimation. Microwave energy will penetrate soil and heat from within, much more efficiently than heating from the surface with radiant heat. This is especially true under vacuum conditions since the heat transfer rate is very low. The depth of microwave penetration is a strong function of the microwave frequency and to a lesser extent on regolith dielectric properties. New methods for delivery of microwaves into lunar and planetary surfaces is being prototyped with laboratory experiments and modeled with COMSOL MultiPhysics. Recent results are discussed.

Ethridge, Edwin↗

Radiative Effect of Springtime Biomass-Burning Aerosols over Northern Indochina During 7-SEAS Baseline 2013 Campaign

The direct aerosol radiative effects of biomass-burning (BB) aerosols over northern Indochina were estimated by using aerosol properties (physical, chemical, and optical) along with the vertical profile measurements from ground-based measurements with integration of an optical and a radiative transfer model during the Seven South East Asian Studies Biomass-Burning Aerosols Stratocumulus Environment: Lifecycles Interactions Experiment (7-SEASBASELInE) conducted in spring 2013. Cluster analysis of backward trajectories showed the air masses arriving at mountainous background site (Doi Ang Khang; 19.93degN, 99.05degE, 1536 m above mean sea level) in northern Indochina, mainly from near-source inland BB activities and being confined in the planetary boundary layer. The PM(sub10) and black carbon (BC)mass were 87 +/- 28 and 7 +/- 2 micrograms m(exp -3), respectively. The aerosol optical depth (AOD (sub 500) was found to be 0.26--1.13 (0.71 +/- 0.24). Finer (fine mode fraction is approximately or equal to 0.95, angstrom-exponent at 440-870 nm is approximately or equal to 1.77) and significantly absorbing aerosols(single scattering albedo is approximately or equal to 0.89, asymmetry-parameter is approximately or equal to 0.67, and absorption AOD 0.1 at 440 nm) dominated over this region. BB aerosols (water soluble and BC) were the main contributor to the aerosol radiative forcing (ARF), while others (water insoluble, sea salt and mineral dust) were negligible mainly due to their low extinction efficiency. BC contributed only 6 to the surface aerosol mass but its contribution to AOD was 12 (2 times higher). The overall mean ARF was 8.0 and -31.4 W m(exp -2) at top-of-atmosphere (TOA) and at the surface (SFC), respectively. Likely, ARF due to BC was +10.7 and -18.1 W m(exp -2) at TOA and SFC, respectively. BC imposed the heating rate of +1.4 K d(exp -1) within the atmosphere and highlighting its pivotal role in modifying the radiation budget. We propose that to upgrade our knowledge on BB aerosol radiative effects in BB source region, the long-term and extensive field measurements are needed.

aerosol optical properties↗

A Global Model for Estimating Atmospheric Phase Scintillation Statistics

Since 2007, the National Aeronautics and Space Administration (NASA) has been collecting atmospheric phase turbulence data from various NASA ground stations throughout the world. The goal of these measurement campaigns has been to generate statistics to characterize the local site turbulence conditions and their impact on widely distributed ground based antenna arrays. This is of critical importance for the situation of uplink arraying, in which a priori knowledge of the fast varying turbulent conditions of water vapor in the troposphere may not be known, and will impact the power combining efficiency of ground based transmitting arrays. Therefore, the design of these type of systems will be dependent on the local climatology of the particular ground station site. Based on the 30+ station years of data collected characterizing atmospheric phase scintillation statistics at various sites, a global model is presented which attempts to predict the average phase statistics of a generic site based on local surface weather data, such as surface pressure, temperature, relative humidity, wind speed, and median wind direction. A model is proposed and based on a standard log power distribution similar to amplitude scintillation models trained on the existing data sets and shows reasonable accuracy against existing data sets.

propagation↗

DirectINJECT: Dosing Systems for Concentrated Liquid Biocides

Reliable and mass-efficient techniques for biocide dosing are necessary to enable residual microbial control in spacecraft potable water systems. DirectINJECT is an approach to provide residual microbial control by injection of concentrated aqueous biocide solution (e.g., highly soluble silver salt), and associated dosing systems technology developments. This would allow for well-controlled liquid biocide injection that requires low consumable mass and is insensitive to the chemistry of the target water. With a 40 g Ag+/l solution, required dosing rates would be ~1 μl/minute during water processing (for a system similar to the ISS WPA), requiring only approximately 20 ml/crew-year of concentrate. We identified and characterized the performance of three dosing systems: pressure-driven flow through a robust micro-capillary tube, a miniature peristaltic pump, and a multi-piston pump with integrated valving. We began to address several potential system reliability concerns including prevention or segregation of gas bubbles in the concentrate reservoirs as well as long-term materials compatibility and mechanical life.

Lance Dean Delzeit↗

DirectINJECT: Dosing Systems for Concentrated Liquid Biocides

Reliable and mass-efficient techniques for biocide dosing are necessary to enable residual microbial control in spacecraft potable water systems. DirectINJECT is an approach to provide ultra-low flow rate injection of stable aqueous biocide concentrate solution (e.g., highly soluble silver salt). This method has the benefit of low consumable mass and is insensitive to the chemistry of the target water. With a 40 g Ag+/liter solution, required dosing rates would be ~1 μl/minute during water processing (for a system similar to the ISS WPA), requiring only approximately 20 ml/crew-year of concentrate. The performance of three dosing systems were identified and characterized: pressure-driven flow through a robust micro-capillary tube with a solenoid valve shut-off, a miniature peristaltic pump, and a multi-piston pump with integrated valving. Several potential system reliability concerns are addressed including prevention or segregation of gas bubbles in the concentrate reservoirs as well as long-term materials compatibility and mechanical life.

silver↗

Biaxial Creep Behavior of Nb-Modified Zircaloys

Zirconium-niobium (Zr-Nb) alloys are used as cladding materials to encapsulate radioactive fuel in nuclear reactors. They possess excellent corrosion resistance at high temperatures making it possible to achieve high fuel burnup, directly increasing the thermal efficiency of the reactor. While they are commonly used in recrystallized (Rx) form in boiling water reactors, there is a need to understand the effect of cold work and stress relief (CWSR) on the biaxial creep characteristics of these materials due to their use in pressurized water reactors. In this study, the biaxial creep behaviors of as-received Zr-Nb alloys, HANA and Zirlo®, have been investigated at 500°C and 400°C, respectively, using internally pressurized tubing superimposed with axial load under varied hoop σθ to axial σz stress ratios of 0 to 2 while monitoring both the axial and hoop strains using a linear variable displacement transformer and a laser telemetric extensometer, respectively. The crystallographic textures and creep loci of these as-received Zr-Nb alloys have been evaluated to correlate with the previous studies on recrystallized HANA4 and CWSR Zircaloy-4. The creep locus of HANA4 was found to be unaffected by initial state (CWSR or Rx) and showed close correspondence to planar isotropy while the creep locus of CWSR Zirlo exhibited more resistance to axial deformation than diametrical as per CWSR Zircaloy-4 reported earlier. These differences are shown to arise from grain-shape anisotropy of the CWSR Zirlo and Zircaloy-4. The simulated creep loci using crystallite-orientation distribution functions in conjunction with prism slip models showed excellent agreement with experimental results.

Tillman, Micah↗

TRANSPORTATION CONSIDERATIONS FOR USED FUEL AND ADVANCED NUCLEAR ENERGY TECHNOLOGIES

This study focuses on requirements and challenges pertaining to advanced transportable nuclear energy systems, which are currently in development and feature varying degrees of mobility. These reactors mostly use high-assay low-enriched uranium (HALEU) fuel, and only limited refueling is required during their lifecycles. Due to the smaller source terms, higher burnup fuel, and potentially higher thermal efficiency involved, the waste inventory will be less than that generated by conventional light-water reactors. However, the relevant regulatory requirements must be met when transporting HALEU fuel (whether fresh or used) inside the reactor vessel—mainly the fuel material transportation, siting, and physical protection requirements outlined in US Nuclear Regulatory Commission (NRC) regulations 10 CFR 71 and 73. Spent nuclear fuel (SNF), as well as irradiated fuel (used during any interval of reactor operation), contains highly radioactive materials that generate heat and necessitate special precautions during transportation. This study addresses the challenges that this incurs, and outlines potential solutions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

TRANSPORTATION CONSIDERATIONS FOR USED FUEL AND ADVANCED NUCLEAR ENERGY TECHNOLOGIES

This study focuses on requirements and challenges pertaining to advanced transportable nuclear energy systems, which are currently in development and feature varying degrees of mobility. These reactors mostly use high-assay low-enriched uranium (HALEU) fuel, and only limited refueling is required during their lifecycles. Due to the smaller source terms, higher burnup fuel, and potentially higher thermal efficiency involved, the waste inventory will be less than that generated by conventional light-water reactors. However, the relevant regulatory requirements must be met when transporting HALEU fuel (whether fresh or used) inside the reactor vessel—mainly the fuel material transportation, siting, and physical protection requirements outlined in US Nuclear Regulatory Commission (NRC) regulations 10 CFR 71 and 73. Spent nuclear fuel (SNF), as well as irradiated fuel (used during any interval of reactor operation), contains highly radioactive materials that generate heat and necessitate special precautions during transportation. This study addresses the challenges that this incurs, and outlines potential solutions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Doubly-Charged Negative Ions as Novel Tunable Catalysts: Graphene and Fullerene Molecules Versus Atomic Metals

The fundamental mechanism underlying negative-ion catalysis involves bond-strength breaking in the transition state (TS). Doubly-charged atomic/molecular anions are proposed as novel dynamic tunable catalysts, as demonstrated in water oxidation into peroxide. Density Functional Theory TS calculations have found a tunable energy activation barrier reduction ranging from 0.030 eV to 2.070 eV, with Si 2– , Pu 2– , Pa 2– and Sn 2– being the best catalysts; the radioactive elements usher in new application opportunities. C 60 2– significantly reduces the standard C 60 – TS energy barrier, while graphene increases it, behaving like cationic systems. According to their reaction barrier reduction efficiency, variation across charge states and systems, rank-ordered catalysts reveal their tunable and wide applications, ranging from water purification to biocompatible antiviral and antibacterial sanitation systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

COVID-19 pandemic ramifications on residential Smart homes energy use load profiles

The COVID-19 pandemic has significantly affected people’s behavioral patterns and schedules because of stay-at-home orders and a reduction of social interactions. Therefore, the shape of electrical loads associated with residential buildings has also changed. In this paper, we quantify the changes and perform a detailed analysis on how the load shapes have changed, and we make potential recommendations for utilities to handle peak load and demand response. Our analysis incorporates data from before and after the onset of the COVID-19 pandemic, from an Alabama Power Smart Neighborhood with energy-efficient/smart devices, using around 40 advanced metering infrastructure data points. This paper highlights the energy usage pattern changes between weekdays and weekends pre– and post–COVID-19 pandemic times. The weekend usage patterns look similar pre– and post–COVID-19 pandemic, but weekday patterns show significant changes. We also compare energy use of the Smart Neighborhood with a traditional neighborhood to better understand how energy-efficient/smart devices can provide energy savings, especially because of increased work-from-home situations. HVAC and water heating remain the largest consumers of electricity in residential homes, and our findings indicate an even further increase in energy use by these systems.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗