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DOE OSTI2024

Constraining gravity with a new precision 𝐸 𝐺 estimator using Planck + SDSS BOSS data

The 𝐸 𝐺 statistic is a discriminating probe of gravity developed to test the prediction of general relativity (GR) for the relation between gravitational potential and clustering on the largest scales in the observable Universe. We present a novel high-precision estimator for the 𝐸 𝐺 statistic using CMB lensing and galaxy clustering correlations that carefully matches the effective redshifts across the different measurement components to minimize corrections. A suite of detailed tests is performed to characterize the estimator’s accuracy, its sensitivity to assumptions and analysis choices, and the non-Gaussianity of the estimator’s uncertainty is characterized. After finalization of the estimator, it is applied to Planck CMB lensing and SDSS CMASS and LOWZ galaxy data. We report the first harmonic space measurement of 𝐸 𝐺 using the LOWZ sample and CMB lensing and also updated constraints using the final CMASS sample and the latest Planck CMB lensing map. We find $\hat{𝐸}$$^{Planck+CMASS}_{𝐺}$ = 0.3⁢6$^{+0.06}_{−0.05}$⁢(68.27%) and $\hat{𝐸}$$^{Planck+LOWZ}_{𝐺}$ = 0.4⁢0$^{+0.11}_{−0.09}$⁢(68.27%), with additional subdominant systematic error budget estimates of 2% and 3%, respectively. Using Ω m,0 constraints from Planck and SDSS BAO observations, Λ⁢CDM-GR predicts 𝐸$^{GR}_ {𝐺}$⁡(𝑧 =0.555) = 0.401 ± 0.005 and 𝐸$^{GR}_{𝐺}$⁡(𝑧 =0.316) = 0.452 ± 0.005 at the effective redshifts of the CMASS and LOWZ based measurements. We report the measurement to be in good statistical agreement with the Λ⁢CDM-GR prediction and report that the measurement is also consistent with the more general GR prediction of scale independence for 𝐸 𝐺 . Furthermore, this work provides a carefully constructed and calibrated statistic with which 𝐸 𝐺 measurements can be confidently and accurately obtained with upcoming survey data.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2017

Compressed Natural Gas Vehicle Maintenance Facility Modification Handbook

To ensure the safety of personnel and facilities, vehicle maintenance facilities are required by law and by guidelines of the National Fire Protection Association (NFPA) and the International Fire Code (IFC) to exhibit certain design features. They are also required to be fitted with certain fire protection equipment and devices because of the potential for fire or explosion in the event of fuel leakage or spills. All fuels have an explosion or fire potential if specific conditions are present. The hazard presented by liquid fuels, such as gasoline and diesel, results from the spillage of these liquids and subsequent ignition of vapors, causing a fire or explosion. Facilities that maintain liquid-fueled vehicles and implement appropriate safety measures are protected with ventilation systems designed to capture liquid fuel vapors at or near floor level. To minimize the potential for ignition in the event of a spill, receptacles, electrical fixtures, and hot-work operations, such as welding, are located outside of these areas. Compressed natural gas (CNG) is composed of methane with slight amounts of heavier simple hydrocarbons. Maintenance facilities that maintain CNG vehicles indoors must be protected against fire and explosion. However, the means of ensuring safety are different from those employed for liquid fuels because of the gaseous nature of methane and the fact that it is lighter than air. Because CNG is lighter than air, a release will rise to the ceiling of the maintenance facility and quickly dissipate rather than remaining at or near floor level like liquid fuel vapors. Although some of the means of protection for CNG vehicle maintenance facilities are similar to those used for liquid-fueled vehicles (ventilation and elimination of ignition sources), the types and placement of the protection equipment are different because of the behavior of the different fuels. The nature of gaseous methane may also require additional safeguards, such as combustible gas detectors and control systems, or specialized space heating, which are not needed in facilities servicing liquid-fuel vehicles. This handbook covers maintenance facilities that service CNG-fueled vehicles. Although similar requirements are mandated for liquefied natural gas (LNG) or liquefied petroleum gas (LPG) fueled vehicles, LNG and LPG are not covered in this handbook.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2011

Secondary waste form testing : ceramicrete phosphate bonded ceramics.

The cleanup activities of the Hanford tank wastes require stabilization and solidification of the secondary waste streams generated from the processing of the tank wastes. The treatment of these tank wastes to produce glass waste forms will generate secondary wastes, including routine solid wastes and liquid process effluents. Liquid wastes may include process condensates and scrubber/off-gas treatment liquids from the thermal waste treatment. The current baseline for solidification of the secondary wastes is a cement-based waste form. However, alternative secondary waste forms are being considered. In this regard, Ceramicrete technology, developed at Argonne National Laboratory, is being explored as an option to solidify and stabilize the secondary wastes. The Ceramicrete process has been demonstrated on four secondary waste formulations: baseline, cluster 1, cluster 2, and mixed waste streams. Based on the recipes provided by Pacific Northwest National Laboratory, the four waste simulants were prepared in-house. Waste forms were fabricated with three filler materials: Class C fly ash, CaSiO{sub 3}, and Class C fly ash + slag. Optimum waste loadings were as high as 20 wt.% for the fly ash and CaSiO{sub 3}, and 15 wt.% for fly ash + slag filler. Waste forms for physical characterizations were fabricated with no additives, hazardous contaminants, and radionuclide surrogates. Physical property characterizations (density, compressive strength, and 90-day water immersion test) showed that the waste forms were stable and durable. Compressive strengths were >2,500 psi, and the strengths remained high after the 90-day water immersion test. Fly ash and CaSiO{sub 3} filler waste forms appeared to be superior to the waste forms with fly ash + slag as a filler. Waste form weight loss was {approx}5-14 wt.% over the 90-day immersion test. The majority of the weight loss occurred during the initial phase of the immersion test, indicative of washing off of residual unreacted binder components from the waste form surface. Waste forms for ANS 16.1 leach testing contained appropriate amounts of rhenium and iodine as radionuclide surrogates, along with the additives silver-loaded zeolite and tin chloride. The leachability index for Re was found to range from 7.9 to 9.0 for all the samples evaluated. Iodine was below detection limit (5 ppb) for all the leachate samples. Further, leaching of sodium was low, as indicated by the leachability index ranging from 7.6-10.4, indicative of chemical binding of the various chemical species. Target leachability indices for Re, I, and Na were 9, 11, and 6, respectively. Degradation was observed in some of the samples post 90-day ANS 16.1 tests. Toxicity characteristic leaching procedure (TCLP) results showed that all the hazardous contaminants were contained in the waste, and the hazardous metal concentrations were below the Universal Treatment Standard limits. Preliminary scale-up (2-gal waste forms) was conducted to demonstrate the scalability of the Ceramicrete process. Use of minimal amounts of boric acid as a set retarder was used to control the working time for the slurry. Flexibility in treating waste streams with wide ranging compositional make-ups and ease of process scale-up are attractive attributes of Ceramicrete technology.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA NTRS2013

Integrating a Microwave Radiometer into Radar Hardware for Simultaneous Data Collection Between the Instruments

The conventional method for integrating a radiometer into radar hardware is to share the RF front end between the instruments, and to have separate IF receivers that take data at separate times. Alternatively, the radar and radiometer could share the antenna through the use of a diplexer, but have completely independent receivers. This novel method shares the radar's RF electronics and digital receiver with the radiometer, while allowing for simultaneous operation of the radar and radiometer. Radars and radiometers, while often having near-identical RF receivers, generally have substantially different IF and baseband receivers. Operation of the two instruments simultaneously is difficult, since airborne radars will pulse at a rate of hundreds of microseconds. Radiometer integration time is typically 10s or 100s of milliseconds. The bandwidth of radar may be 1 to 25 MHz, while a radiometer will have an RF bandwidth of up to a GHz. As such, the conventional method of integrating radar and radiometer hardware is to share the highfrequency RF receiver, but to have separate IF subsystems and digitizers. To avoid corruption of the radiometer data, the radar is turned off during the radiometer dwell time. This method utilizes a modern radar digital receiver to allow simultaneous operation of a radiometer and radar with a shared RF front end and digital receiver. The radiometer signal is coupled out after the first down-conversion stage. From there, the radar transmit frequencies are heavily filtered, and the bands outside the transmit filter are amplified and passed to a detector diode. This diode produces a DC output proportional to the input power. For a conventional radiometer, this level would be digitized. By taking this DC output and mixing it with a system oscillator at 10 MHz, the signal can instead be digitized by a second channel on the radar digital receiver (which typically do not accept DC inputs), and can be down-converted to a DC level again digitally. This unintuitive step allows the digital receiver to sample both the radiometer and radar data at a rapid, synchronized data rate (greater than 1 MHz bandwidth). Once both signals are sampled by the same digital receiver, high-speed quality control can be performed on the radiometer data to allow it to take data simultaneously with the radar. The radiometer data can be blanked during radar transmit, or when the radar return is of a power level high enough to corrupt the radiometer data. Additionally, the receiver protection switches in the RF front end can double as radiometer calibration sources, the short (four-microsecond level) switching periods integrated over many seconds to estimate the radiometer offset. The major benefit of this innovation is that there is minimal impact on the radar performance due to the integration of the radiometer, and the radiometer performance is similarly minimally affected by the radar. As the radar and radiometer are able to operate simultaneously, there is no extended period of integration time loss for the radiometer (maximizing sensitivity), and the radar is able to maintain its full number of pulses (increasing sensitivity and decreasing measurement uncertainty).

McLinden, Matthew↗

DOE OSTI2024

Carbonate Management to Enable Energy- and Carbon-Efficient CO 2 Electrolysis (Final Technical Report)

The rapid growth and plummeting cost of solar energy have spurred growing interest in using CO 2 electrolysis to produce chemicals and fuels as an alternative to conventional petrochemical processes. High-temperature (>800 °C) solid oxide electrolyzers that convert CO 2 into CO and O 2 have recently become commercially available. Low-temperature electrolysis cells offer the prospect of more convenient and flexible operation, which is critical for utilizing intermittent solar energy, and provide access to more valuable C 2+ products such as ethylene, ethanol, and propanol. Over the past 10 years, research in this area has yielded substantial progress in both fundamental understanding of the requisite electrocatalytic reactions and design of prototype devices. Leveraging insights from fuel cells and membrane water electrolyzers, researchers have developed electrolysis cells with gas diffusion electrodes (GDE) that have demonstrated high CO 2 electrolysis current densities (>100 mA cm –2 ) as well as promising selectivity and stability. Despite these advances, the energy efficiency (electrical energy-to-product) and carbon efficiency (CO 2 -to-product) of low-temperature CO 2 electrolysis remain far too low for large-scale deployment. A preponderance of evidence indicates that the principal source of efficiency losses is the rapid and thermodynamically favorable reaction of CO 2 with hydroxide (OH – ) to form carbonate (CO 3 2– ). Carbonate formation imposes steady-state electrolysis conditions that result in large voltage and CO 2 losses for all known (photo)electrochemical CO 2 cells. While much current research remains focused on CO 2 reduction catalyst design, this largely overlooked CO 3 2– problem presents a fundamental scientific barrier to creating a viable electrochemical option for converting solar energy into chemicals and fuels. The project pursues an integrated, multi-PI research effort that establishes a fundamental science of CO 3 2– management. PI Kanan and Co-PI Mani’s contribution to the project is to evaluate strategies to mitigate the CO 3 2– problem by changing the properties of the electrolyte and the environment in which CO 2 reduction catalysis takes place. Experimental studies showed that electrolytes composed of a high concentration of both CO 3 2– and HCO 3 – , which serve as moderately alkaline buffers, improved the cell voltage by compared to all-HCO 3 – electrolytes, but these buffered systems still show substantial CO 2 uptake that reduces pH over time. Computational studies developed a homogenized model of a CO 2 reduction catalyst layer that permits a low-cost exploration of the high-dimensional parameter space associated with catalyst layers on gas diffusion electrodes. The model was validated by accurately reproducing experimental data for the related but simpler reaction of CO reduction and then used to probe the effects of catalyst layer architecture on CO 2 reduction. Minimizing the size of catalyst and hydrophobic domains in the catalyst layer is predicted to mitigate CO 3 2– formation and thereby enable prolonged operation at elevated pH. In support of the CO 2 electrolysis studies, a new method for rapidly prototyping electrochemical cells was developed and validated. The method uses a combination of 3D printing and electroless plating to generate conductive cell components for evaluating new cell designs. The carbonate problem encompasses mass transport processes and acid-base reactions that are relevant to many other electrochemical systems. Investigation of strategies to address the carbonate problem led to an additional line of inquiry into the physicochemical phenomena that determine the efficiency of electrochemical acid-base production, which has numerous applications in the broader field of carbon management. New strategies for using the supporting electrolyte to inhibit H + /OH – recombination in electrochemical acid-base production were evaluated, leading to the development of a novel acid-base producing system that eliminates the need for ion exchange membranes and exhibits promising efficiency and current densities for scalable applications.

25 ENERGY STORAGE↗

DOE OSTI2012

The potential role of a carbon tax in U.S. fiscal reform

This paper examines fiscal reform options in the United States with an intertemporal computable general equilibrium model of the world economy called G-Cubed. Six policy scenarios explore two overarching issues: (1) the effects of a carbon tax under alternative assumptions about the use of the resulting revenue, and (2) the effects of alternative measures that could be used to reduce the budget deficit. We examine a simple excise tax on the carbon content of fossil fuels in the U.S. energy sector starting immediately at $15 per metric ton of carbon dioxide (CO2) and rising at 4 percent above inflation each year through 2050. We investigate policies that allow the revenue from the illustrative carbon tax to reduce the long run federal budget deficit or the marginal tax rates on labor and capital income. We also compare the carbon tax to other means of reducing the deficit by the same amount. We find that the carbon tax will raise considerable revenue: $80 billion at the outset, rising to $170 billion in 2030 and $310 billion by 2050. It also significantly reduces U.S. CO2 emissions by an amount that is largely independent of the use of the revenue. By 2050, annual CO2 emissions fall by 2.5 billion metric tons (BMT), or 34 percent, relative to baseline, and cumulative emissions fall by 40 BMT through 2050. The use of the revenue affects both broad economic impacts and the composition of GDP across consumption, investment and net exports. In most scenarios, the carbon tax lowers GDP slightly, reduces investment and exports, and increases imports. The effect on consumption varies across policies and can be positive if households receive the revenue as a lump sum transfer. Using the revenue for a capital tax cut, however, is significantly different than the other policies. In that case, investment booms, employment rises, consumption declines slightly, imports increase, and overall GDP rises significantly relative to baseline through about 2040. Thus, a tax reform that uses a carbon tax to reduce capital taxes would achieve two goals: reducing CO2 emissions significantly and expanding short-run employment and the economy. We examine three ways to reduce the deficit by an equal amount. We find that raising marginal tax rates on labor income has advantages over raising tax rates on capital income or establishing a carbon tax. A labor tax increase leaves GDP close to its baseline, reduces consumption very slightly and expands net exports slightly. Investment remains essentially unchanged. In contrast, a capital tax increase causes a significant and persistent drop in investment and much larger reductions in GDP. A carbon tax falls between the two: it lowers GDP more than a labor tax increase because it reduces investment. However, its effects on investment and GDP are more moderate than the capital tax increase, and it also significantly reduces CO2 emissions. A carbon tax thus offers a way to help reduce the deficit and improve the environment, and do so with minimal disturbance to overall economic activity.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

DOE OSTI2011

Annual Site Environmental Report: 2010 (ASER)

This report provides information about environmental programs during the calendar year of 2010 at the SLAC National Accelerator Laboratory (SLAC), Menlo Park, California. Activities that overlap the calendar year - i.e., stormwater monitoring covering the winter season of 2010/2011 (October 2010 through May 2011) are also included. SLAC is a federally-funded research and development center with Stanford University as the M&O contractor. Under Executive Order (EO) 13423, Strengthening Federal Environmental, Energy, and Transportation Management, EO 13514, Federal Leadership in Environmental, Energy, and Economic Performance, and DOE Order 450.1A, Environmental Protection Program, SLAC effectively implements and integrates the key elements of an Environmental Management System (EMS) to achieve the site's integrated safety and environmental management system goals. For normal daily activities, SLAC managers and supervisors are responsible for ensuring that policies and procedures are understood and followed so that: (1) Worker safety and health are protected; (2) The environment is protected; and (3) Compliance is ensured. Throughout 2010, SLAC continued to improve its management systems. These systems provided a structured framework for SLAC to implement 'greening of the government' initiatives such as EO 13423, EO 13514, and DOE Orders 450.1A and 430.2B. Overall, management systems at SLAC are effective, supporting compliance with all relevant statutory and regulatory requirements. During 2010, there were no reportable releases to the environment from SLAC operations. In addition, many improvements in waste minimization, recycling, stormwater management, groundwater restoration, and SLAC's chemical management system (CMS) were continued. The following are among SLAC's environmental accomplishments for 2010. To facilitate management and identification of future potential greenhouse gases (GHG) reduction opportunities, SLAC voluntarily completed GHG inventories for calendar year (CY) 2008 and CY 2009 and submitted the results to The Climate Registry. A Lead Management Plan was completed to reduce the potential of lead impacting the environment, and two large legacy tube-trailer modules, each containing 38 tubes of compressed ethane, were reused or recycled by an outside contractor, resulting in hazardous waste avoidance and cost savings of approximately $100,000 in transportation and disposal costs. SLAC continues to make progress on achieving the sustainability goals of EOs 13423 and 13514, which include, but are not limited to reductions in the use of water, energy, and fuel, building to green standards and reductions in GHG emissions. Phase I of the SLAC Advanced Metering project for electrical and natural gas systems was completed. Phase I included the design of the metering system and purchase of the enterprise software. The planning, design, and installation of an advanced water metering system for select buildings, landscape, and process systems were completed. In addition, the last major onsite chiller containing a Class I ozone-depleting substance was taken out of service, and SLAC continued to replace conventional vehicles with electric vehicles. In 2010, there were no radiological impacts to the public or the environment from SLAC operations. The potential doses to the public were negligible and far below the regulatory and SLAC administrative limits. No radiological incidents occurred that increased radiation levels to the public or released radioactivity to the environment. In addition to managing its radioactive wastes safely and responsibly, SLAC worked to reduce the amount of waste generated. SLAC shipped 2,891 cubic feet of low-level radioactive waste, half of which was legacy waste, to appropriate treatment and disposal facilities for low-level radioactive waste. SLAC also continued its efforts to reduce the inventory of materials no longer needed for its mission by permanently removing 125 sealed radioactive sources from the inventory. Ninety-seven of the sealed sources were returned to the manufacturer, and 28 were sent to Energy Solutions for processing before being sent to the Nevada Test Site for burial. In addition, 87 concrete blocks which had been stored in an area known as the Bone Yard were surveyed for potential surface contamination and volumetric activation prior to off-site release. Based on the comprehensive measurements, all 87 blocks were qualified for release and were disposed of as ordinary materials at a landfill. In 2010, the SLAC Environmental Restoration Program personnel continued work on site characterization and evaluation of remedial alternatives at four sites with volatile organic compounds in groundwater and several areas with polychlorinated biphenyls and low concentrations of lead in soil.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA NTRS2012

The Pursuit of K: Reflections on the Current State-of-the-Art in Stress Intensity Factor Solutions for Practical Aerospace Applications

The elastic stress intensity factor (SIF, commonly denoted as K) is the foundation of practical fracture mechanics (FM) analysis for aircraft structures. This single parameter describes the first-order effects of stress magnitude and distribution as well as the geometry of both structure/component and crack. Hence, the calculation of K is often the most significant step in fatigue analysis based on FM. This presentation will provide several reflections on the current state-of-the-art in SIF solution methods used for practical aerospace applications, including a brief historical perspective, descriptions of some recent and ongoing advances, and comments on some remaining challenges. Newman and Raju made significant early contributions to practical structural analysis by developing closed-form SIF equations for surface and corner cracks in simplified geometries, often based on empirical fits of finite element (FE) solutions. Those solutions (and others like them) were sometimes revised as new analyses were conducted or limitations discovered. The foundational solutions have exhibited striking longevity, despite the relatively "coarse" FE models employed many decades ago. However, in recent years, the accumulation of different generations of solutions for the same nominal geometry has led to some confusion (which solution is correct?), and steady increases in computational capabilities have facilitated the discovery of inaccuracies in some (not all!) of the legacy solutions. Some examples of problems and solutions are presented and discussed, including the challenge of maintaining consistency with legacy design applications. As computational power has increased, the prospect of calculating large numbers of SIF solutions for specific complex geometries with advanced numerical methods has grown more attractive. Fawaz and Andersson, for example, have been generating literally millions of new SIF solutions for different combinations of multiple cracks under simplified loading schemes using p-version FE methods. These data are invaluable, but questions remain about their practical use, because the tabular databases of key results needed to support practical life analysis can occupy gigabytes of storage for only a few classes of geometries. The prospect of using such advanced numerical methods to calculate in real time only those K solutions actually needed to support a specific crack growth analysis is also tempting, but the stark reality is that the computational cost is still so high that the approach is not practical except for specific, critical application problems. Some thoughts are offered about alternative paradigms. Compounding approaches are some of the earliest building blocks of SIF development for more complex geometries. These approaches are especially attractive because of their very low computational cost and their conceptual robustness; they are, in some ways, an intriguing contrast and complement to the brute-force numerical methods. In recent years, researchers at NRC-Canada have published remarkable results showing how compounding approaches can be used to generate accurate solutions for very difficult problems. Examples are provided of some successes--and some limitations--using this approach. These closed-form, tabulated numerical, and compounding approaches have typically been used for simple remote loading with simple load paths to the crack. However, many significant cracks occur in complex stress gradient fields. This is a job for weight function (WF) methods, where the arbitrary stress distribution on the crack plane in the corresponding uncracked body (typically determined using FE methods) is used to determine K. Several significant recent advances in WF methods and solutions are highlighted here. Fueled by advanced 3D numerical methods, many new solutions have been generated for classic geometries such as surface and corner cracks with wide ranges of geometrical validity. A new WF formulation has also be developed for part-through cracks considering the arbitrary stress gradients in all directions in the crack plane (so-called bivariant solutions). Basic WF methods have recently been combined with analytical expressions for crack plane stresses to develop a large family of accurate SIF solutions for corner, surface, and through cracks at internal or external notches with very wide ranges of shapes, sizes, acuities, and offsets. Finally, WF solutions are much faster than FE or boundary element solutions, but can still be much slower than simple closed-form solutions, especially for bivariant solutions that can require 2D numerical integration. Novel pre-integration and dynamic tabular methods have been developed that substantially increase the speed of these advanced WF solutions. The practical utility of advanced SIF methods, including both WF and direct numerical methods, is greatly enhanced if the FM life analysis can be directly and efficiently linked with digital models of the actual structure or component (e.g., FE models for stress analysis). Two recent advances of this type will be described. One approach directly interfaces the FM life analysis with the FE model of the uncracked component (including stress results). Through a powerful graphical user interface, simplified FM life models can be constructed (and visualized) directly on the component model, with the computer collecting the geometry and stress gradient information needed for the life calculation. An even more powerful paradigm uses expert logic to automatically build an optimum simple fracture model at any and every desired location in the component model, perform the life calculation, and even generate fatigue crack growth life contour maps, all with minimal user intervention. This paradigm has also been extended to the automatic calculation of fracture risk, considering uncertainty or variability in key input parameters such as initial crack size or location. Another new integrated approach links the engineering life analysis, the component model, and a 3D numerical fracture analysis built with the same component model to generate a table of SIF values at a specific location that can then be employed efficiently to perform the life calculation. Some attention must be given to verification and validation (V&V) issues and challenges: how good are these SIF solutions, how good is good enough, and does anyone believe the life answer? It is important to think critically about the different sources of error or uncertainty and to perform V&V in a hierarchal, building-block manner. Some accuracy issues for SIF solutions, for example, may actually involve independent material behavior issues, such as constraint loss effects for crack fronts near component surfaces, and can be a source of confusion. Recommendations are proposed for improved V&V approaches. This presentation will briefly but critically survey the range of issues and advances mentioned above, with a particular view towards assembling an integrated approach that combines different methods to create practical tools for real-world design and analysis problems. Examples will be selectively drawn from the recent literature, from recent enhancements in the NASGRO and DARWIN computer codes, and from previously unpublished research

CraigMcClung, R.↗

NASA NTRSDate not supplied

In-Situ Reaction Monitoring for Lunar Applications Utilizing a Single Quadrupole Residual Gas Analyzer

With a revived focus to create a permeant presence on the moon and in preparation for future Mars exploration, it is imperative that all re-sources are utilized to their fullest potential. In-Situ Resource Utilization (ISRU) will be critical for future mission success as it would enable independent operation of missions while minimally relying on the complex supply chain created between the Earth, moon and Mars. One of the most critical resources that have been identified for ISRU is the creation of liquid oxygen (O2) for not only breathable air, but also for rocket fuel. On the moon and potentially Mars, one of the most O2 rich resources is in the presence of regolith. Although there are numerous minerals within regolith and various processes to extract O2, this is not the scope of this paper. Since the O2 extraction method can vary, a critical standardized analytical method is needed to verify O2 (or oxygenated precursor compounds) for extraction efficiency and purity. Our group utilizes a modified consumer off-the-shelf (COTS), Residual Gas Analyzer (RGA) Single Quadrupole Mass Spectrometer (QMS). Due to the current field mission requirements, the gas analysis module will need to rely only on mass-to-charge ratios (m/z) and peak intensities to differentiate and quantitate targeted gas-phase reactants or products, i.e. carbon monoxide (CO), carbon dioxide (CO2), methane (CH4) and hydrogen (H2). However, due to solar wind implanted volatiles and various other compounds present in lunar regolith, such as nitrogen (N2), helium (He), and deuterium (D2), deconvolution and quantification of isobaric compounds becomes quite difficult. Specifically, the presence of N2 makes quantification of CO, an oxygenated precursor, difficult due to both compounds having a peak at m/z 28. Approaches to differentiate isobaric components: Initially, the solution to overcome isobaric overlap was to use isotopic ratios, particularly be-tween carbon-13 and nitrogen-15. Although limited literature discuss isotopic composition and attempt to quantify the ratios, variation is particularly high and limited to a few lunar regolith samples. The following were identified as potential approaches to quantify isobaric species, N2 and CO, using our RGA. Threshold Ionization. CO and N2 both have peaks at m/z 28, but only N2 is capable of producing a peak at m/z 7. While a N2 peak at m/z 7 is generally rare, instrument parameters can be optimized in order to maximize the peak intensity. Typically a standard ionization energy of 70 eV is used to monitor a batch process and would produce reliable results for a majority of the reactants or products that we are interested in quantifying. However, to analyze the rare molecular fragment of N2 (N2+ at m/z 7), a different ionization energy may be beneficial. Threshold Ionization Mass Spectrometry (TIMS) will be explored to optimize the N2+ peak at m/z 7 by varying parameters such as ionization energy and pressure. Therefore, a quantitative value at m/z 7 will be used to determine the product gas concentration of N2, which will be subtracted from the total concentration determined at m/z 28 enabling us to approximate the amount of CO. Secondary Detector (infrared gas detector, IR). Another approach to quantitate and differentiate be-tween isobaric components is to leverage alternative modes of detection. Unlike mass spectrometry, which generally uses a separation step prior to analysis (i.e. gas chromatography), IR produces energy that is specifically absorbed depending on the bond and configuration of the molecule. This technique could be leveraged since it is generally only active on non-symmetric molecules, i.e. CO. Utilizing concentrations of CO determined from another detector could help correct concentrations of CO obtained from the QMS. However, the inclusion of another detector adds additional mission requirements, such as power, software changes and avionics updates that add additional cost and schedule requirements.

mass spectrometry↗

DOE OSTI2013

Development of Technologies and Capabilities for Coal Energy Resources

This is the final report for the Aerojet Rocketdyne (AR) Advanced Gasification Systems Development (AGSD) project that was initiated on October 1, 2004. The project’s primary objective is to demonstrate technologies that improve the availability and efficiency of gasification-based power plants and to reduce plant capital and operational costs. The objective will be accomplished by (1) development and testing of cooled refractory liners, (2) feed system development and demonstration, (3) pilot plant definition and planning, (4) transport gasifier feed analysis, (5) coal-biomass mixture feed analysis, and (6) coal-biomass mixture pilot scale tests. Task 1, development and testing of cooled refractory liners, was conducted at CANMET Energy Technology Centre in Ottawa, Canada. The test objectives were to screen high conductivity CMC materials with alternate manufacturing methods and a variety of surface treatments for cooled metal tubes in a slagging gasifier environment. During the CMC testing, it was found that a constantly cooled CMC will survive in good conditions and that high porosity CMC resulted in high material erosion and corrosion. During cooled tube testing, it was found that hard metal spray coat and bare Haynes 188 performed the best. Task 2, feed system development and demonstration, was conducted at at the Energy and Environmental Research Center (EERC) at the University of North Dakota (UND). For tasks 2.1-2.6, the test objective was to demonstrate 400-tons/day coal feed system operation (to 1,000 psia gasifier pressures) in ultra-dense phase flow without plugging and to achieve multi-element injector flow-split non-uniformities below 2 %RSD. Testing was successfully completed with no feed system plugging of the feed system. The majority of the other Task 2 activities were associated with the Dry Solids Pump design (Task 2.8 and 2.11), development (Task 2.10), fabrication (Task 2.12), amd testing (Task 2.13-2.15). A variety of tests were performed that verified the capability of the Dry Solids Pump to consolidate various pulverized feedstocks to a state capable of sealing and sustaining downstream outlet pressures during mechanical operation of the pump as well as during periods when the pump was turned off. However, the final operating goals were not achieved. Task 3, pilot plant definition and planning, was to define requirements for an advanced commercial gasifier with a cooled liner and to establish a preferred commercial gasifier system configuration to serve as the reference point for an advanced gasifier pilot plant concept definition. A pilot plant concept was successfully defined that is scalable and traceable to the commercial gasifier configuration. The schedule and cost for design, installation, and long-duration test operation of a pilot plant were estimated at 33 months and $\$$25.6M. Taks 4, transport gasifier feed analysis, was to determine the effects of larger sized transport gasifier low rank coals within the AR dry solids pump. It was found for the two low-rank +100 mesh size transport gasifier coals that the cohesion of these larger materials was significantly less than the coals ground to minus 200 mesh. Also, the gas permeability of the MSL transport coal was found to be significantly higher than the permeability of the PRB transport coal. Task 5, coal-biomass mixture feed analysis, was to determine the effects of coal biomass blends within the AR ultra-dense phase feed system and dry solids pump, and to determine the cost of electricity increase of an integrated gasification combined cycle (IGCC) operating on coal/biomass blends with the AR dry solids pump and ultra-dense phase feed system. In summary, it was found that 75/25 wt% coal/corn stover blends produce reasonable economic results for IGCC operation with minimal dry solids pump modifications – especially if the coal is a low rank coal and the corn stover biomass is pelletized. The increase in electricity cost was found to be 1.1 cents/kWh. Task 6, coal-biomass mixture pilot scale tests, was to determine which coal/biomass blends could be tested in the current dry solids pump without major modifications. As reported in detail in the reports by Sprouse (2010) and Sprouse and Darby (2013), the coal/biomass blend having the least impact on pump configuration and operation is the 90/10 wt% Illinois #6 to corn stover ratio blend. The AGSD program was initiated on October 1, 2004. The interim final report was submitted on October 21, 2010 and covered Task 1, Task 2.1-2.9, and Task 3, performed during budget period 1. This final report covers Task 2.10-2.16, 4, 5, and 6, performed during budget period 2. The interim final report is attached as part of the appendix to this report.

Darby, Alan K.↗

DOE OSTI2020

Uranium Mill Tailings Radiation Control Act Title II DOE Due Diligence and Lessons Learned from a Previous Site Transfer - 20352

Title II of the Uranium Mill Tailings Radiation Control Act (UMTRCA) established that a government agency will provide perpetual care for closed uranium and thorium ore-processing sites that were operating under an NRC source material license in 1978 or were licensed thereafter. Commercial owners (licensees) operating under an NRC or agreement state specific license when UMTRCA was passed are responsible for conducting reclamation of any byproduct material remaining from uranium-ore processing operations in accordance with an NRC or agreement state approved reclamation plan. Reclamation includes both surface and groundwater remedies. Upon completion of reclamation and approval by NRC, the site is required to be transferred to either the host state or the DOE for long-term surveillance and maintenance. Since UMTRCA's enactment, six Title II sites have been transferred to DOE; an additional 24 Title II sites are anticipated to be transferred before 2050. DoE's role mandated under UMTRCA Title II as the long-term care custodian is to perform 'monitoring, maintenance, and emergency measures necessary to protect the public health and safety.' UMTRCA requires that the licensee pay a long-term surveillance charge 'sufficient to cover the annual costs of site surveillance.' However, at some sites such as the Bluewater, New Mexico, Disposal Site, this mandate has required additional effort and expense by DOE, beyond the originally anticipated and intended scope within UMTRCA, but within the authority of DOE under UMTRCA. In 1997, the Bluewater site became the second UMTRCA Title II site to be transferred to DOE. The site was the location of a uranium mill operated from 1953 until 1982. The specific licensee began site reclamation in 1991, and by 1995 all tailings and contaminated materials were encapsulated in two tailings disposal cells and other disposal areas. In addition to surface contamination, milling activities impacted groundwater in the two upper aquifers. In 1989, the specific licensee attempted active groundwater remediation; however, no significant reduction in contaminant concentrations was observed. As a result, the specific licensee applied to NRC for alternate concentration limits (ACLs) in 1990, which were approved in 1996 as being protective, after additional corrective actions were performed. Since transfer of the Bluewater site to DOE, unforeseen challenges have occurred, requiring additional actions. The first challenge is the occurrence of surface depressions located on the northern section of the main tailings disposal cell. The depressions were first observed during DoE's initial inspection in 1998; however, evidence of these can be observed on satellite images taken prior to transfer. Since being first observed, the depressions have continued to grow both in depth and areal extent. Due to the design of the main tailings disposal cell, the depressions impede storm water from being effectively shed off the 101- hectare (250-acre) top slope of the main tailings disposal cell. Instead, storm water accumulates in the depressions, forming a large ephemeral pond that has stored up to 16.3 x 10{sup 6} liters (4.3 million gallons) of stormwater. The ponding poses a potential risk to the integrity of the main tailings disposal cell in the case of a large storm event, with the potential to cause the pond to overtop and erode the cover material and underlying waste. DOE has taken a number of short-term actions to monitor, measure, and reduce the ponding and is currently working with the US Army Corps of Engineers to design and construct a repair. Additional challenges are associated with groundwater at the Bluewater site. Nine wells were present on the 1335-hectare (3300-acre) site upon transfer. Groundwater compliance was called into question after the State of New Mexico reduced its uranium groundwater standard from 5.0 to 0.03 milligrams per liter in 2004, and when an ACL for uranium was exceeded in a site monitoring well in 2010. Acquiring historical groundwater data and subsequent evaluations as well as additional DOE groundwater monitoring led to installing 10 new monitoring wells and performing additional site hydrogeology recharacterization. DOE continues to evaluate groundwater conditions at the site and works with the NRC to determine regulatory requirements and a path forward. As a result of lessons learned at the Bluewater site and other Title II sites, improved processes have been implemented at a programmatic level to increase due diligence before site transfer and prevent similar issues from occurring at other UMTRCA Title II sites under long-term management. DoE's due diligence process is documented in the Process for Transition of UMTRCA Title II Disposal Sites to DOE for Long-Term Surveillance and Maintenance and is designed to ensure that DOE has no technical or compliance concerns with regulatory decisions that might compromise protectiveness following site transfer to DOE. Implementation of the due diligence process has increased DoE's role prior to site transfer and has been effective in identifying potential issues. Actions by NRC and specific licensees, in response to enhanced due diligence efforts by DOE, are expected to minimize, if not totally prevent, the need for unanticipated actions by DOE pertaining to the surface and groundwater remedies after site transfer. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

AN ACID BAKING APPROACH TO ENHANCE RARE EARTH ELEMENT RECOVERY FROM BITUMINOUS COAL SOURCES

Rare earth elements (REE) are a group of 17 elements typically classified as light and heavy rare earth elements, which play a crucial role in developing the latest technologies for energy, defense, and medical sectors. Even though REEs have been found in more than 200 minerals, only bastnaesite, monazite and xenotime are commercially exploited for REE extraction. However, the recent exponential increase in REE demand has spurred countries such as the United States into research for the extraction of REEs from secondary sources such as coal, acid mine drainage, and coal ash. Several coal sources (e.g., Fire Clay seam coal) across the United States have been identified to contain elevated concentrations of rare earth elements (>600 ppm), and various researchers have investigated the feasibility of both physical and hydrometallurgical extraction techniques for rare earth concentration and subsequent extraction. However, both physical and direct leaching were concluded to be inefficient for RE beneficiation and extraction due to low recoveries. Alternatively, thermal treatment provides promising means for RE recovery from bituminous coal sources. The positive impact of thermal treatment/calcination was established to be due to the decarbonization and dehydroxylation of the clays, which released entrapped rare earth elements within the dominant minerals and converted them into an acid-soluble form. Nonetheless, the improvement in recovery was limited to the light REEs (LREEs) with an insignificant increase in the heavy REEs (HREE). It was demonstrated that the light and heavy REEs in the material were associated with difficult-to-leach minerals such as monazite, xenotime, and zircon, which were not decomposed by simple calcination due to their high thermal stability. Hence, roasting in the presence of chemicals was necessary to ensure the decomposition of those REE-containing minerals. As such, this study was focused on the acid baking treatment of bituminous coals with an aim to enhance REE recovery, especially HREEs. Based on the presence of REE minerals like monazite and xenotime, three pre-leach treatment methods, i.e., 1) roasting, 2) direct acid baking, and 3) acid baking after roasting were investigated. Roasting tests at 600 ⁰C revealed that the recovery of light REEs (LREEs) was enhanced while the recovery of HREEs remained relatively unaffected. LREE and HREE recovery values of 38.3% and 21.3%, respectively, were achieved using a 50 g/L sulfuric acid solution at 5% solid concentration and a solution temperature of 75 ⁰C for 2 hours. Comparatively, direct acid baking at 250 °C provided substantial increased LREE and HREE recovery values to approximately 49.4% and 53.0%, respectively, using an equivalent acid dosage. Recoveries were maximized to 77.0% and 79.6% for LREE and HREE, respectively, by roasting followed by acid baking. Similar results were obtained from the treatment of a second bituminous coal source. Due to strong correlations between REE and Al recovery values, tests were performed on kaolinite and illite, which were prominent clay minerals within the source coals. These experiments revealed that the REE recovery improvements were likely a result of dehydroxylation of clays and subsequent release and decomposition of REE-bearing minerals such as monazite, xenotime and zircon. Subsequently, a parametric study was conducted to identify the impact of acid baking parameters on rare earth element recovery. The factors investigated using a three-level statistical experimental program were acid baking time, acid solution concentration, baking temperature, and acid solution-to-solids ratio which were found to significantly impact REE and contaminant element (Al, Fe, and Ca) recovery. An increase in baking temperature up to around 250 ⁰C improved the light and heavy REE recovery values by more than 50 absolute percentage points relative to performances achieved when direct leaching. As aforementioned, acid baking was needed to both decompose the clay minerals and liberate the REE minerals, which allowed access for the acid to solubilize the REEs. Acid concentration of the solution used for acid baking was studied as a means of minimizing the amount of acid needed to achieve a target REE recovery. However, thermo-gravimetric and differential scanning calorimetry analysis (TGA-DSC) of sulfuric acid under oxidizing atmosphere revealed that the addition of water decreased the evaporation temperature, which explains the lower REE recovery values obtained when using acid concentrations less than 100%. Using pure sulfuric acid at an acid-to-solid ratio of 0.8:1 resulted in recovery values of around 70% for both LREEs and HREEs. The decomposition reaction time was relatively quick with 65% of the TREEs recovered within the first 10 minutes. Following the identification of optimum operating conditions through the parametric study, a systematic leaching study was carried out to examine the impact of leaching parameters, such as solid-to-liquid (S/L) ratio, temperature, and time, on REE recovery using acid baking conditions of 1:1 acid to solids ratio at 250 °C for 30 minutes. The solid-to-liquid ratio was varied from 1-20% by weight at 25 °C, 50 °C, and 75 °C solution temperatures. The results indicated that reaction time and solution temperature considerably impacted the recovery of heavy and light REEs. Interestingly, LREE recovery reduced from 68% at 5% S/L to 58% at 20%S/L, whereas HREE recovery of 78% remained unaffected. The decrease in the LREE recovery was determined to be due to La and Ce precipitation, likely through isomorphic substitution with calcium in gypsum. The kinetic data indicated that 67% LREE and 77% HREE recovery could be obtained within the first 15 minutes of the reaction, suggesting fast reaction kinetics. Furthermore, raising the solution temperature from 25 °C to 75 °C increased the LREE and HREE recovery from 60% and 32% to 67% and 79%, respectively. The kinetic modeling results demonstrated that the rate-limiting step in the LREE dissolution was diffusion and chemical reaction, whereas the HREE extraction was controlled by only chemical reaction. The leaching study concluded that using 20% S/L at 75 °C for 15 minutes maximized LREE and HREE recovery. The lab-scale precipitation study showed that Fe and Al in solution could be removed at pH 4.5 followed by REE precipitation at pH 6.0 using 6 mol/L NaOH. Finally, the bench-scale data was used to develop a process flowsheet for REE recovery from low-grade bituminous coal sources using acid baking. Finally, based on the proposed flowsheet, a concentrated RE-cake obtained through selective precipitation at pH 6.5 was re-leached using HCl at pH 1.5. The resultant leachate was used to identify the impact of various operating parameters on REE recovery and purity with an aim to maximize REE precipitation efficiency while minimizing the oxalic acid dosage. The operating parameters for this investigation were oxalic acid dosage, iron (III) contamination, solution pH and temperature. The resultant model suggested that oxalic acid dosage and reaction pH are the most significant factors for the REE precipitation efficiency, followed by the interaction of oxalic dosage and Fe concentration. Test results indicated that increasing the oxalic acid concentration from 0g/L to 80g/L improved the REE precipitation efficiency from approximately 4.2% to 95.0%. Furthermore, raising the solution pH from 0.5 to 2.5 considerably enhanced the precipitation efficiency from 0.0% to 98.9%. A solution temperature elevation decreased REE recovery, which indicated an exothermic reaction between REEs and oxalate anions. Finally, a high level of Fe contamination adversely impacted REE precipitation efficiency. The speciation analysis revealed that the dominant iron species in the solution system were Fe-(C₂O₄)₃³⁻, Fe-(C₂O₄)²⁻, and Fe-(C₂O₄)⁺, which consumed the majority of the oxalate anions

rare earth elements, acid baking, high-temperature↗

DOE OSTI2020

Antifoam Development for Eliminating Flammability Hazards and Decreasing Cycle Time in the Defense Waste Processing Facility

The Savannah River National Laboratory (SRNL) was requested to develop a new antifoam control method for the Defense Waste Processing Facility’s (DWPF) Chemical Process Cell (CPC). SRNL completed testing of both chemical and nonchemical foam controls. The nonchemical foam controls were either ineffective (or worse, created more foam) or impractical (a water spray can control foam, but excessive water is needed). As a result, the focus of this study was on finding a superwetter or commercial antifoam for controlling foam. Thirty potential antifoams were tested as part of this study. A series of tests were developed to help screen out ineffective alternatives including: 1. Spreading testing of superspreaders, 2. Foam column testing with physical simulants, 3. Boiling testing with physical and chemical simulants, 4. Days-only Sludge Receipt and Adjustment Tank (SRAT) process simulations with sludge (containing noble metals and mercury), Precipitate Reactor Feed Tank (PRFT), and Slurry Mix Evaporator Feed Tank (SEFT) simulants in the RC1 Reaction Calorimeter (purchased for antifoam testing), and 5. Around-the-clock SRAT and Slurry Mix Evaporator (SME) process simulations with sludge(containing noble metals and mercury), PRFT, and SEFT simulants in the RC1 Reaction Calorimeter. Evonik Surfynol® MD20, a commercially available defoamer, was relatively effective in controlling foam, while remaining chemically stable in SRAT and SME processing across the pH range of 4 to 13. No degradation products were detected in the offgas, in the condensate or in the SRAT and SME products. In nitric-glycolic acid flowsheet testing, 250 mg/kg Evonik Surfynol® MD20 was needed for foam control compared to 1,625 mg/kg for Antifoam 747, DWPF’s current antifoam. In nitric-formic acid flowsheet testing, 1,125 mg/kg of Evonik Surfynol® MD20 was needed to control foam throughout the SRAT and SME cycles. The commercially available superspreader Momentive™ Y-17112 was even more effective than Evonik Surfynol® MD20 as both a defoamer and an antifoam. Not only was the foam destroyed upon addition but also was less persistent between additions. It was the most effective antifoam in testing using both the nitric-glycolic acid flowsheet and the nitric-formic acid flowsheet. In nitric-glycolic acid flowsheet testing, only 100 mg/kg Momentive™ Y-17112 was needed to control foam throughout the SRAT and SME cycles. In nitric-formic acid flowsheet testing, 300 mg/kg Momentive™ Y-17112 was needed to control foam throughout the SRAT and SME cycles. Momentive™ Y-17112 is also resistant to hydrolysis as demonstrated by its chemical stability in SRAT and SME processing across the pH range of 4 to 13 and lack of degradation products in offgas or condensate. Both candidates were effective as potential replacements for Antifoam 747, with Y-17112 demonstrating superior foam control. During nitric-glycolic flowsheet testing 50% less antifoam was needed when using Momentive™ Y-17112 compared to MD20. During nitric-formic flowsheet testing 75% less antifoam was needed when using Momentive™ Y-17112 compared to MD20. Foam remediated with Momentive™ Y-17112 was less persistent throughout testing. In addition, no degradation products were detected in the offgas, in the condensate or in the SRAT and SME products. Based on this testing, Momentive™ Y-17112 is clearly superior to Evonik Surfynol® MD20 and Antifoam 747, especially for the nitric-formic acid flowsheet processing; it is recommended that Momentive™ Y-17112 replace Antifoam 747 in DWPF. An antifoam addition strategy is recommended for both the nitric-glycolic acid flowsheet and the nitric-formic acid flowsheet. Implementation of Momentive™ Y-17112 is expected to decrease SRAT and SME boiling times by up to 50%, eliminate the issues resulting from Antifoam 747 degradation products, and minimize foamovers. To validate the effectiveness of these defoaming agents, SRNL recommends irradiation of a SRAT or SME product simulant containing fresh antifoam. The goal of this testing is to determine whether the irradiation causes decomposition of the antifoam that would make it less effective or produce new species in the offgas or slurry. This testing began in April 2020. An evaluation should be completed to determine the thermolytic hydrogen and methane generation rate in downstream equipment, including the High-Level Waste evaporators.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2014

LABORATORY OPTIMIZATION TESTS OF TECHNETIUM DECONTAMINATION OF HANFORD WASTE TREATMENT PLANT LOW ACTIVITY WASTE OFF-GAS CONDENSATE SIMULANT

The Hanford Waste Treatment and Immobilization Plant (WTP) Low Activity Waste (LAW) vitrification facility will generate an aqueous condensate recycle stream (LAW Off-Gas Condensate) from the off-gas system. The baseline plan for disposition of this stream is to send it to the WTP Pretreatment Facility, where it will be blended with LAW, concentrated by evaporation and recycled to the LAW vitrification facility again. Alternate disposition of this stream would eliminate recycling of problematic components, and would enable de-coupled operation of the LAW melter and the Pretreatment Facilities. Eliminating this stream from recycling within WTP would also decrease the LAW vitrification mission duration and quantity of glass waste. This LAW Off-Gas Condensate stream contains components that are volatile at melter temperatures and are problematic for the glass waste form. Because this stream recycles within WTP, these components accumulate in the Condensate stream, exacerbating their impact on the number of LAW glass containers that must be produced. Approximately 32% of the sodium in Supplemental LAW comes from glass formers used to make the extra glass to dilute the halides to acceptable concentrations in the LAW glass, and diverting the stream reduces the halides in the recycled Condensate and is a key outcome of this work. Additionally, under possible scenarios where the LAW vitrification facility commences operation prior to the WTP Pretreatment facility, identifying a disposition path becomes vitally important. This task examines the potential treatment of this stream to remove radionuclides and subsequently disposition the decontaminated stream elsewhere, such as the Effluent Treatment Facility (ETF), for example. The treatment process envisioned is very similar to that used for the Actinide Removal Process (ARP) that has been operating for years at the Savannah River Site (SRS), and focuses on using mature radionuclide removal technologies that are also compatible with longterm tank storage and immobilization methods. For this new application, testing is needed to demonstrate acceptable treatment sorbents and precipitating agents and measure decontamination factors for additional radionuclides in this unique waste stream. The origin of this LAW Off-Gas Condensate stream will be the liquids from the Submerged Bed Scrubber (SBS) and the Wet Electrostatic Precipitator (WESP) from the LAW melter off-gas system. The stream is expected to be a dilute salt solution with near neutral pH, and will likely contain some insoluble solids from melter carryover. The soluble components are expected to be mostly sodium and ammonium salts of nitrate, chloride, and fluoride. This stream has not been generated yet and will not be available until the WTP begins operation, but a simulant has been produced based on models, calculations, and comparison with pilot-scale tests. One of the radionuclides that is volatile and expected to be in greatest abundance in this LAW Off-Gas Condensate stream is Technetium-99 ({sup 99}Tc). Technetium will not be removed from the aqueous waste in the Hanford WTP, and will primarily end up immobilized in the LAW glass by repeated recycle of the off-gas condensate into the LAW melter. Other radionuclides that are low but are also expected to be in measurable concentration in the LAW Off-Gas Condensate are {sup 129}I, {sup 90}Sr, {sup 137}Cs, {sup 241}Pu, and {sup 241}Am. These are present due to their partial volatility and some entrainment in the off-gas system. This report discusses results of optimized {sup 99}Tc decontamination testing of the simulant. Testing examined use of inorganic reducing agents for {sup 99}Tc. Testing focused on minimizing the quantity of sorbents/reactants added, and minimizing mixing time to reach the decontamination targets in this simulant formulation. Stannous chloride and ferrous sulfate were tested as reducing agents to determine the minimum needed to convert soluble pertechnetate to the insoluble technetium dioxide. The reducing agents were tried with and without sorbents. The sorbents, hydroxyapatite and sodium oxalate, were expected to sorb the precipitated technetium dioxide and facilitate removal. The Phase 1 tests examined a broad range of conditions and used the initial baseline simulant. The Phase 2 tests narrowed the conditions based on Phase 1 results, and used a slightly modified simulant. Test results indicate that excellent removal of {sup 99}Tc was achieved using SnCl{sub 2} as a reductant, and was effective with or without sorption onto hydroxyapatite. This reaction worked even in the presence of air (which could oxidize the stannous ion) and at room temperature. This process was very effective at neutral pH, with a Decontamination Factor (DF) >199 in one hour with only 1 g/L of SnCl{sub 2}. Prior work had shown that it was much less effective at alkaline pH. The only deleterious effect observed was that the chromium co-precipitates with the {sup 99}c during the SnCl{sub 2} reduction. This effect was anticipated, and would have to be considered when managing disposition paths of this stream. Reduction using FeSO{sub 4} was not effective at removing {sup 99}Tc, but did remove the Cr. Chromium is present due to partial volatility and entrainment in the off-gas, and is highly oxidizing, so would be expected to react with reducing agents more quickly than pertechnetate. Testing showed that sufficient reducing agent must be added to completely reduce the chromium before the technetium is reduced and removed. Other radionuclides are also present in this off-gas condensate stream. To enable sending this stream to the Hanford ETF, and thereby divert it from the recycle where it impacts the LAW glass volume, several of these also need to be removed. Samples from optimized conditions were also measured for actinide removal in order to examine the effect of the Tc-removal process on the actinides. Plutonium was also removed by the SnCl{sub 2} precipitation process. Results of this separation testing indicate that sorption/precipitation is a viable concept and has the potential to decontaminate the {sup 99}Tc from the stream, allowing it to be diverted away from WTP and thus eliminating the impact of the recycled halides and sulfate on the LAW glass volume. Based on the results, a possible treatment scenario could involve the use of a reductive precipitation agent (SnCl{sub 2}) with or without sorbent at neutral pH to remove the Tc. Although hydroxyapatite was not necessary to effect the {sup 99}Tc removal, it may be beneficial in solid-liquid separations. Other testing will examine removal of the other radionuclides. This testing was the second phase of testing, which aimed at optimizing the process by examining the minimum amount of reductant needed and the minimum reaction time. Although results indicated that SnCl{sub 2} was effective, further work on a pH-adjusted Fe(SO{sub 4}) mixture are needed. Additional tasks are needed to examine removal of the other radionuclides, solid-liquid separation technologies, slurry rheology measurements, composition variability impacts, corrosion and erosion, and slurry storage and immobilization.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2026

Investigation of Flux Spreading in a Light-Trapping, Planar-Cavity Receiver for Enclosed Solar Particle Heating

Concentrating solar thermal power (CSP) technology development has recently focused on increasing the operating temperatures to accommodate high efficiency power cycles and thermochemical processes. Inert solid particles as heat transfer media enable solar receivers to operate above 700 degrees Celsius resulting in increased system thermal efficiency compared to the conventional molten salt based CSP system. An open-cavity falling-particle solar receiver that can efficiently heat particles by direct heating from concentrated solar radiation faces challenges with large particle losses from wind and unable to support thermochemical reactions. A light-trapping, planar cavity reiver (LTPCR) where particles are indirectly heated can significantly minimize the particle losses during the operation, support thermochemical reactions, and offer scalability potential. The LTPCR features an array of vertical planar receiver/absorber panels arranged within a cavity configuration. Concentrated solar radiation from heliostats is focused onto the receiver walls, where heat is indirectly transferred to solid particles flowing inside the receiver channels. Heat transfer occurs through direct contact between the receiver panel walls and particles, and can be enhanced by fluidizing particles with air. This fluidization increases particle-wall contact and extends particle residence time, maximizing heat transfer efficiency. The unique vertical planar receiver structure originated from a near-blackbody tubular light absorber, effectively distributing the incoming solar beam spread across the panel walls and trapping light. This flux spreading effect, driven by cosine projection, converts high incident solar flux into a lower, more uniform heat flux on the panel walls. This redistribution enhances heat transfer efficiency between particle-wall or reaction gases-wall, while preventing localized overheating of the receiver panel. Indirect planar cavity solar receivers completely separate solid particles from the ambient environment that can greatly reduce the thermal losses in heated particles resulting in high efficiency at high temperatures above 700 degrees Celsius. This design ensures no particle losses to the environment during the operation while open-cavity designs can experience significant particle losses from wind. An experimental investigation was conducted to observe flux spreading on the receiver panel wall. A lab-scale prototype planar receiver, fabricated using Haynes 230 alloy, was tested under direct concentrated solar radiation using the high-flux solar furnace (HFSF) facility at NREL. The experiment was performed under normal peak radiative heat fluxes ranging from 800 to 1900 kW/m2. A temperature distribution on the panel wall was measured using a thermal imaging camera (FLIR A 6600). To prevent overheating at the receiver front tip, prism-shaped heat shields (Zircar UNIFROM C1) were placed in front of the receiver, and their influence on flux spreading was also studied. Absorbed flux distribution on the panel wall was modeled using SolTrace. The total solar power and flux distributions delivered from HFSF were determined based on the heliostat mirror optical properties, direct normal irradiance (DNI) on the on-sun testing days, peak flux measurement during the on-sun testing, and shutter/attenuator settings Due to the large incident angles of the solar beam on the panel wall, the angular optical properties of Haynes 230 alloy and Zircar heat shields were incorporated into the model. This flux distribution model was then integrated into a computational fluid dynamics (CFD) simulation to predict the receiver panel wall temperature, which was compared with the experimental measurements. Both prediction and measurements identified a temperature hotspot at the backside of the panel, indicating that the incident solar beam can fully reach to the rear of the receiver. The heat shields positioned at the front of the receiver effectively reduced the excessive temperature rise at the receiver front tip. Overall, the temperature was well distributed over the panel wall, with a minor hotspot at the back of the receiver. The model slightly overpredicted the temperature, possibly due to discrepancies in optical properties of the panel and an underprediction of thermal loss in the receiver. The advancement of the particle LTPCR offers a viable alternative to open-cavity receivers by addressing particle loss issues. Additionally, it presents a pathway for enabling solar thermochemical processes, extending CSP technology beyond power generation to fuel and chemical production.

14 SOLAR ENERGY↗

DOE OSTI2011

The use of commercial and industrial waste in energy recovery systems - A UK preliminary study

Highlights: > Commercial and industrial waste samples collected. > Samples analysed for calorific value, moisture, ash and elemental composition. > Values similar to those of municipal solid waste and refuse derived fuel. > Sampled waste could be used in current energy recovery systems with minimal retrofitting. > Sampled waste could account 6.5% towards the UK's 2020 renewable electricity target if all qualifying waste is used. - Abstract: With 2020 energy targets set out by the EU fast approaching, the UK is trying to source a higher proportion of its energy from renewable resources. Coupled with this, a growing population and increasing trends in consumer demand have resulted in national waste loads increasing. A possible solution to both issues is energy-from-waste (EfW) technologies. Many studies have focused on municipal solid waste (MSW) as a potential feedstock, but appear to overlook the potential benefits of commercial and industrial waste (C and IW). In this study, samples of C and IW were collected from three North West waste management companies and Lancaster University campus. The samples were tested for their gross and net calorific value, moisture content, ash content, volatile matter, and also elemental composition to determine their suitability in EfW systems. Intra-sample analysis showed there to be little variation between samples with the exception two samples, from waste management site 3, which showed extensive variation with regards to net calorific value, ash content, and elemental analysis. Comparisons with known fuel types revealed similarities between the sampled C and IW, MSW, and refuse derived fuel (RDF) thereby justifying its potential for use in EfW systems. Mean net calorific value (NCV) was calculated as 9.47 MJ/kg and concentrations of sulphur, nitrogen, and chlorine were found to be below 2%. Potential electrical output was calculated using the NCV of the sampled C and IW coupled with four differing energy generation technologies. Using a conventional incinerator with steam cycle, total electrical output was calculated as 24.9 GWh, based on a plant operating at 100,000 tpa. This value rose to 27.0 GWh when using an integrated gasification combined cycle. A final aspect of this study was to deduce the potential total national electrical output if all suitable C and IW were to be used in EfW systems. Using incineration coupled with a steam turbine, this was determined to be 6 TWh, 1.9% of the national demand thereby contributing 6.5% towards the UK's 2020 renewable electricity target.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

NASA NTRS2003

Design and Testing of Non-Toxic RCS Thrusters for Second Generation Reusable Launch Vehicle

The current NASA Space Shuttle auxiliary propulsion system utilizes nitrogen tetroxide (NTO) and monomethylhydrazine (MMH), hypergolic propellants. This use of these propellants has resulted in high levels of maintenance and precautions that contribute to costly launch operations. By employing alternate propellant combinations, those less toxic to humans, the hazards and time required between missions can be significantly reduced. Use of alternate propellants can thereby increase the efficiency and lower the cost in launch operations. In support of NASA's Space Launch Initiative (SLI), TRW proposed a three-phase project structured to significantly increase the technology readiness of a high-performance reaction control subsystem (RCS) thruster using non-toxic propellant for an operationally efficient and reusable auxiliary propulsion system (APS). The project enables the development of an integrated primary/vernier thruster capable of providing dual-thrust levels of both 1000-lbf class thrust and 25-lbf thrust. The intent of the project is to reduce the risk associated with the development of an improved RCS flight design that meets the primary NASA objectives of improved safety and reliability while reducing systems operations and maintenance costs. TRW proposed two non-toxic auxiliary propulsion engine designs, one using liquid oxygen and liquid hydrogen and the other using liquid oxygen and liquid ethanol, as candidates to meet the goals of reliability and affordability at the RCS level. Both of these propellant combinations offer the advantage of a safe environment for maintenance, while at the same time providing adequate to excellent performance for a conventional liquid propulsion systems. The key enabling technology incorporated in both TRW thrusters is the coaxial liquid on liquid pintle injector. This paper will concentrate on only the design and testing of one of the thrusters, the liquid oxygen (LOX) and liquid hydrogen (LH2) thruster. The LOX/LH2 thruster design includes a LOX-centered pintle injector, consisting of two rows of slots that create a radial spoke spray pattern in the combustion chamber. The main fuel injector creates a continuous sheet of LH2 originating upstream of the LOX pintle injector. The two propellants impinge at the pintle slots, where the resulting momentum ratio and spray pattern determines the combustion efficiency and thermal effects on the hardware. Another enabling technology used in the design of this thruster is fuel film cooling through a duct, lining the inner wall of the combustion chamber barrel section. The duct is also acts as a secondary fuel injection point. The variation in the amount of LH2 used for the duct allows for adjustments in the cooling capacity for the thruster. The Non-Toxic LOX-LH2 RCS Workhorse Thruster was tested at the NASA Marshall Space Flight Center's Test Stand 500. Hot-fire tests were conducted between March 08, 2002 and April 05, 2002. All testing during the program base period were performed at sea-level conditions. During the test program, 7 configurations were tested, including 2 combustion chambers, 3 LOX injector pintle tips, and 4 LH2 injector stroke settings. The operating conditions that were surveyed varied thrust levels, mixture ratio and LH2 duct cooling flow. The copper heat sink chamber was used for 16 burns, each burn lasting from 0.4 to 10 seconds, totaling 51.4 seconds, followed by Haynes chamber testing ranging from 0.9 to 120 seconds, totaling 300.9 seconds. The total accumulated burn time for the test program is 352.3 seconds. C* efficiency was calculated and found to be within expectable limits for most operating conditions. The temperature on the Haynes combustion chamber remained below established material limits, with the exception of one localized hot spot. The test results demonstrate that both the coaxial liquid-on-liquid pintle injector design and fuel duct concepts are viable for the intended application. The thruster head-e design maintained cryogenic injection temperatures while firing, which validates the concept for minimal heat soak back. By injecting fuel into the duct, the throat temperatures were manageable, yet the split of fuel through the cooling duct does not compromise the overall combustion efficiency, which indicates that, provided proper design refinement, such a concept can be applied to a high-performance version of the thruster. These hot fire tests demonstrate the robustness of the duct design concept and good capability to withstand off-nominal operating conditions without adversely impacting the thermal response of the engine, a key design feature for a cryogenic thruster.

Calvignac, Jacky↗

NASA NTRS2019

Field Evaluations of Sampling, Interviewing, and Flight Tracking of NASA's Low Boom Flight Demonstrator Aircraft

The first year’s effort identified sampling and interviewing as the principal risks to assessment of prompt reactions to overflights producing low-amplitude sonic booms. It also 1) established the utility of geo-information system-based route planning for LBFD flight missions, 2) developed and demonstrated a prototype of a geographically-distributed, Internet-enabled instrumentation system capable of wide-area tracking of LBFD aircraft in near-real time. The latter system permits synchronizing the conduct of interviews in multiple overflown communities with arrival times of shock waves at interviewing sites; and of measuring, archiving, and processing their acoustic signatures. Means were also recommended for constructing representative, telephone-based samples of eligible respondents living in households within carpet boom corridors adjacent to LBFD flight tracks, and for conducting interviews with cross-sectional (independent) samples of such respondents about their prompt reactions to exposure to low-amplitude sonic booms. A detailed study design was prepared and accepted by NASA for a set of single-contact attempt telephone interviews with a nationally representative sample of households. The study design focused on testing automated and live agent interview completion rates obtainable without callbacks. A minimal (two monitoring station) version of the aircraft tracking system was built and installed near a civil airport in a successful demonstration of the system’s ability to detect and track aircraft movements. The field exercise also demonstrated the ability of the system to capture the acoustic emissions of departing aircraft, and to serve aircraft position and sound level information to remote, geographically-distributed analysts in near-real time. Upon approval of OMB and IRB of the detailed study plan, a stratified, nationally representative sample of landline and wireless telephone-subscribing households was constructed. A total of 12,734 telephone interview contact attempts of the sort required by a straightforward cross-sectional study design were then made. These contact attempts demonstrated the impracticality of conducting a time-critical, cross-sectional study of prompt community response to low-amplitude sonic booms by means of “independent” (single contact attempt per respondent for each LBFD flight mission) telephone samples of respondents. The observed interview completion rates for these single telephone contact attempts were so low (~ 1% to 3% for automated and live agent interviews, respectively) that: 1) the representativeness of collected opinions would be susceptible to intuitive challenge as inadequate, even absent conclusive evidence of non-representativeness. Refuting challenges to representativeness would have to demonstrate that the composition of the actual sample did not differ from that of the target population, a task that is tantamount to proving a negative; 2) the information required to refute allegations of non-representativeness would require a questionnaire considerably lengthier than that required simply to determine the prevalence of boom-induced startle and annoyance. Such a questionnaire would have to inquire about potentially sensitive and intrusive matters, including respondents’ age, gender, education, employment, home ownership, income, ethnicity, family size, and other demographic factors; and 3) unreasonable numbers of attempts would be required to re-contact households with unsuccessful initial contact attempts, given the limited time available for doing so. For example, if about 500 completed interviews were desired in a supersonically overflown community, approximately 50,000 automated interview attempts would have to be made within ten to fifteen minutes of each LBFD overflight. Such large numbers of contact attempts could well exceed the numbers of households available for interview in areas of similar boom exposure levels in some communities near LBFD flight tracks. Such large numbers of interviews could be cost-effectively undertaken only by means of automated (i.e., outgoing interactive voice response) interviewing, a data collection method ill-suited for complex and sensitive questionnaire items. The infeasibility of independent sampling for evaluating prompt responses to LBFD overflights in a cross-sectional study is due in large part to simple non-response: that is, potential respondents – particularly those contacted on wireless telephones – refusing to answer calls with unfamiliar caller IDs. It is also due in part, however, to 1) the lack of time to attempt to contact the same respondent more than once within a few minutes after the arrival of a shock wave at the respondent’s location; and 2) the need to place calls during weekday/daytime hours, when response rates are notably lower than during evenings and weekends. Despite the poor interview completion rates achieved under the above constraints, cross sectional assessments of delayed reactions to LBFD overflights could still be feasible, if multiple attempts could be made to contact respondents during evening and weekend time periods, over extended time periods. Detailed plans for a longitudinal (panel) sample were developed as an alternative to a cross sectional sample design.

Fidell, Sanford↗

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