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At least 1,369 records · Page 76

Spinel dissolution via addition of glass forming chemicals. Results of preliminary experiments

Increased loading of high level waste in glass can lead to crystallization within the glass. Some crystalline species, such as spinel, have no practical impact on the chemical durability of the glass, and therefore may be acceptable from both a processing and a product performance standpoint. In order to operate a melter with a controlled amount of crystallization, options must be developed for remediating an unacceptable accumulation of crystals. This report describes preliminary experiments designed to evaluate the ability to dissolve spinel crystals in simulated waste glass melts via the addition of glass forming chemicals (GFCs).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Biological Upcycling of Plastics Waste

Plastic wastes accumulate in the environment, impacting wildlife and human health and representing a significant pool of inexpensive waste carbon that could form feedstock for the sustainable production of commodity chemicals, monomers, and specialty chemicals. Current mechanical recycling technologies are not economically attractive due to the lower-quality plastics that are produced in each iteration. Thus, the development of a plastics economy requires a solution that can deconstruct plastics and generate value from the deconstruction products. Biological systems can provide such value by allowing for the processing of mixed plastics waste streams via enzymatic specificity and using engineered metabolic pathways to produce upcycling targets. We focus on the use of biological systems for waste plastics deconstruction and upcycling. We highlight documented and predicted mechanisms through which plastics are biologically deconstructed and assimilated and provide examples of upcycled products from biological systems. Additionally, we detail current challenges in the field, including the discovery and development of microorganisms and enzymes for deconstructing non–polyethylene terephthalate plastics, the selection of appropriate target molecules to incentivize development of a plastic bioeconomy, and the selection of microbial chassis for the valorization of deconstruction products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

EBS Task Force: Task 9/FEBEX Modeling Final Report: Thermo-Hydrological Modeling with PFLOTRAN

This report outlines Sandia National Laboratories modeling studies applied to Stage 1 and Stage 2 of the Full-scale Engineered Barriers Experiment in Crystalline Host Rock (FEBEX) in situ test for the SKB EBS Task Force Task 9. The FEBEX test was a full-scale test conducted over ~18 years at the Grimsel, Switzerland Underground Research Laboratory (URL) managed by NAGRA. It involved emplacing simulated waste packages, in the form of welded cylindrical heaters, inside a tunnel in crystalline granitic rock and surrounded by a bentonite barrier and cement plug. Sensors emplaced within the bentonite monitored the wetting-up, heating, and drying out of the bentonite barrier, and the large resulting data set provides an excellent opportunity for validation of multiphysics Thermal-Hydrological (TH), Thermal-Hydrologic-Chemical (THC), and Thermal-Hydrological-Mechanical (THM) modeling approaches for underground nuclear waste storage and the performance of engineered bentonite barriers. The present status of the EBS Task Force is finalizing Task 9, which follows years of modeling studies of the FEBEX test, by many notable modeling teams (Gens et al., 2009; Sanchez et al. 2010; 2012; Samper et al., 2018). These modeling studies generally use two-dimensional axisymmetric meshes, ignoring threedimensional effects, gravity and asymmetric wetting and dry out of the bentonite engineered barrier. This study investigates these effects with use of the PFLOTRAN THC code with massively parallel computational methods in modeling FEBEX Stage 1 and Stage 2 results. The PFLOTRAN numerical code is an open source, state-of-the-art, massively parallel subsurface flow and reactive transport code operating in a high-performance computing environment (Hammond et al., 2014). Section 2 describes the applied partial differential equations describing mass, momentum and energy balance used in this study, considerations derived by assuming phase equilibrium between gas and liquid phases, constitutive equations for granite, cement plug, and bentonite domains, and specific approaches for use inthe PFLOTRAN code. Section 3 describes the geometry, meshing, and model set-up. Section 4 describes modeling results, Section 5 compares modeling results to field testing data, and Section 6 gives conclusions. The Appendix provides detailed information required by the EBSTask Force for final reporting.

42 ENGINEERING↗

Using polymerization, glass structure, and quasicrystalline theory to produce high level radioactive borosilicate glass remotely: a 20+ year legacy

Vitrification is currently the most widely used technology for the treatment of high level radioactive wastes (HLW) throughout the world. Most of the nations that have generated HLW are immobilizing in borosilicate glass. One of the primary reasons that glass has become the most widely used immobilization media is the relative simplicity of the vitrification process, e.g. melt a highly variable waste with some glass forming additives such as SiO 2 and B 2 O 3 in the form of a premelted frit and pour the molten mixture into a stainless steel canister. Seal the canister before moisture can enter the canister (10’ tall by 2’ in diameter) so the canister does not corrode from the inside out. Glass has also become widely used for HLW is that due to the fact that the short range order (SRO) and medium range order (MRO) found in the structure of glass atomistically bonds the radionuclides and hazardous species in the waste. The SRO and MRO have also been found to govern the melt properties such as viscosity and resistivity of the melt and the crystallization potential and solubility of certain species. Furthermore, the molecular structure of the glass also controls the glass durability, i.e. the contaminant/radionuclide release, by establishing the distribution of ion exchange sites, hydrolysis sites, and the access of water to those sites. The molecular structure is flexible and hence accounts for the flexibility of glass formulations to HLW waste variability. Nuclear waste glasses melt between 1050-1150°C which minimizes the volatility of radioactive components such as 99 Tc, 137 Cs, and 129 I. Nuclear waste glasses have good long term stability including irradiation resistance. Process control models were developed based on the molecular structure of glass, polymerization theory of glass, and quasicrystalline theory of glass crystallization. These models create a glass which is durable, pourable, and processable with 95% accuracy without knowing from batch to batch what the composition of the waste coming out of the storage tanks will be. These models have operated the Savannah River Site Defense Waste Processing Facility (SRS DWPF), which is the world’s largest HLW Joule heated ceramic melter, since 1996. This unique “feed forward” process control, which qualifies the durability, pourability, and processability of the waste plus glass additive mixture before it enters the melter, has enabled ~8000 tons of HLW glass and 4242 canisters to be produced since 1996 with only one melter replacement.

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Process for the production of ultrahigh purity silane with recycle from separation columns

Tri- and dichlorosilanes formed by hydrogenation in the course of the reaction of metallurgical silicon, hydrogen and recycle silicon tetrachloride are employed as feed into a separation column arrangement of sequential separation columns and redistribution reactors which processes the feed into ultrahigh purity silane and recycle silicon tetrachloride. A slip stream is removed from the bottom of two sequential columns and added to the recycle silicon tetrachloride process stream causing impurities in the slip streams to be subjected to reactions in the hydrogenation step whereby waste materials can be formed and readily separated.

Coleman, Larry M.↗

A History of the Environmental Management Advisory Board: 20 Years of Service and Partnership - 13219

The Environmental Management Advisory Board (EMAB or Board) was chartered under the Federal Advisory Committee Act (FACA) in 1992 to provide the Assistant Secretary for Environmental Management (EM) with independent and external advice, information, and recommendations on corporate issues relating to accelerated site clean-up and risk reduction throughout the EM complex. Over the course of the past 20 years, the composition and focus of the Board have varied widely to address the changing needs of the program. EMAB began as the Environmental Restoration and Waste Management Advisory Committee, formed to provide advice on an EM Programmatic Environmental Impact Statement. In 1994, the Board was restructured to function more as an executive-level, limited member advisory board whose membership provides insight of leading industry experts and the viewpoints of representatives from critical stakeholder constituencies. Throughout the 20 years of its existence, EMAB has covered a wide variety of topics and produced nearly 200 recommendations. These recommendations have resulted in several policy changes and improvements within EM. Most recently, EMAB has been credited for its contribution to the EM Energy Park Initiative, forerunner of the DOE Asset Revitalization Initiative; creation of the EM Offices of Communications and External Affairs; improvement of acquisition and project management strategies and culture; and several recommendations related to the Waste Treatment Plant and the tank waste programs at Hanford and the Savannah River Site. The wealth of experience and knowledge the Assistant Secretary can leverage through utilization of the Board continues to support fulfillment of EM's mission. In commemoration of EMAB's 20. anniversary, this paper will provide further context for the evolution of the Board, the role FACA plays in its administration, and a look at the members' current objectives and EM's expectations for the future. (authors)

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Kinetics of Cold-Cap Reactions for Vitrification of Nuclear Waste Glass Based on Simultaneous Differential Scanning Calorimetry - Thermogravimetry (DSC-TGA) and Evolved Gas Analysis (EGA)

For vitrifying nuclear waste glass, the feed, a mixture of waste with glass-forming and modifying additives, is charged onto the cold cap that covers 90-100% of the melt surface. The cold cap consists of a layer of reacting molten glass floating on the surface of the melt in an all-electric, continuous glass melter. As the feed moves through the cold cap, it undergoes chemical reactions and phase transitions through which it is converted to molten glass that moves from the cold cap into the melt pool. The process involves a series of reactions that generate multiple gases and subsequent mass loss and foaming significantly influence the mass and heat transfers. The rate of glass melting, which is greatly influenced by mass and heat transfers, affects the vitrification process and the efficiency of the immobilization of nuclear waste. We studied the cold-cap reactions of a representative waste glass feed using both the simultaneous differential scanning calorimetry thermogravimetry (DSC-TGA) and the thermogravimetry coupled with gas chromatography-mass spectrometer (TGA-GC-MS) as complementary tools to perform evolved gas analysis (EGA). Analyses from DSC-TGA and EGA on the cold-cap reactions provide a key element for the development of an advanced cold-cap model. It also helps to formulate melter feeds for higher production rate.

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Treatment of LLW Components for Waste Minimization and Recycling - 16258

The Studsvik Melting Facility has been in operation for almost 30 years. Many turbines, heat exchangers and other retired components, pipes, structures have been treated in the facility during those years. The ambition of all projects is to minimize the waste volumes for final disposal and to maximize the amount of material that can be recycled. Another objective, respecting ALARA, is to keep dose exposition to the personnel at very low levels. The overall concept comprises the whole sequence of preparations from road and sea transports, the management of the metallic LLW by segmentation, decontamination and sorting using specially devised tools and shielded treatment cell, to the decision criteria for recycling of the metals, radiological analyses and conditioning of the residual waste into a final form suitable for customer-related disposal. The records show that the amount of material possible for conditional clearance to open market after treatment is between 95 - 97 % on weight for falling metallic scrap. For large components there is a larger span and especially for heat exchangers. This paper describes the Studsvik technical concept and experience related to treatment of metals from the program for modernization and power upgrade of the Swedish nuclear power plants. (authors)

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Application of evolved gas analysis to cold-cap reactions of melter feeds for nuclear waste vitrification

In the vitrification of nuclear wastes, the melter feed (a mixture of nuclear waste and glass-forming and modifying additives) experiences multiple gas-evolving reactions in an electrical glass-melting furnace. We employed the thermogravimetry-gas chromatography-mass spectrometry (TGA-GC-MS) combination to perform evolved gas analysis (EGA). Apart from identifying the gases evolved, we performed quantitative analysis relating the weighed sum of intensities of individual gases linearly proportional with the differential themogravimetry. The proportionality coefficients were obtained by three methods based on the stoichiometry, least squares, and calibration. The linearity was shown to be a good first-order approximation, in spite of the complicated overlapping reactions.

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DETERMINATION OF HLW GLASS MELT RATE USING X-RAY COMPUTED TOMOGRAPHY

The purpose of the high-level waste (HLW) glass melt rate study is two-fold: (1) to gain a better understanding of the impact of feed chemistry on melt rate through bench-scale testing, and (2) to develop a predictive tool for melt rate in support of the on-going frit development efforts for the Defense Waste Processing Facility (DWPF). In particular, the focus is on predicting relative melt rates, not the absolute melt rates, of various HLW glass formulations solely based on feed chemistry, i.e., the chemistry of both waste and glass-forming frit for DWPF. Critical to the successful melt rate modeling is the accurate determination of the melting rates of various HLW glass formulations. The baseline procedure being used at the Savannah River National Laboratory (SRNL) is to; (1) heat a 4 inch-diameter stainless steel beaker containing a mixture of dried sludge and frit in a furnace for a preset period of time, (2) section the cooled beaker along its diameter, and (3) measure the average glass height across the sectioned face using a ruler. As illustrated in Figure 1-1, the glass height is measured for each of the 16 horizontal segments up to the red lines where relatively large-sized bubbles begin to appear. The linear melt rate (LMR) is determined as the average of all 16 glass height readings divided by the time during which the sample was kept in the furnace. This 'visual' method has proved useful in identifying melting accelerants such as alkalis and sulfate and further ranking the relative melt rates of candidate frits for a given sludge batch. However, one of the inherent technical difficulties of this method is to determine the glass height in the presence of numerous gas bubbles of varying sizes, which is prevalent especially for the higher-waste-loading glasses. That is, how the red lines are drawn in Figure 1-1 can be subjective and, therefore, may influence the resulting melt rates significantly. For example, if the red lines are drawn too low, a significant amount of glassy material interspersed among the gas bubbles will be excluded, thus underestimating the melt rate. Likewise, if they are drawn too high, many large voids will be counted as glass, thus overestimating the melt rate. As will be shown later in this report, there is also no guarantee that a given distribution of glass and gas bubbles along a particular sectioned plane will always be representative of the entire sample volume. Poor reproducibility seen in some LMR data may be related to these difficulties of the visual method. In addition, further improvement of the existing melt rate model requires that the overall impact of feed chemistry on melt rate be reflected on measured data at a greater quantitative resolution on a more consistent basis than the visual method can provide. An alternate method being pursued is X-ray computed tomography (CT). It involves X-ray scanning of glass samples, performing CT on the 2-D X-ray images to build 3-D volumetric data, and adaptive segmentation analysis of CT results to not only identify but quantify the distinct regions within each sample based on material density and morphologies. The main advantage of this new method is that it can determine the relative local density of the material remaining in the beaker after the heat treatment regardless of its morphological conditions by selectively excluding all the voids greater than a given volumetric pixel (voxel) size, thus eliminating much of the subjectivity involved in the visual method. As a result, the melt rate data obtained from CT scan will give quantitative descriptions not only on the fully-melted glass, but partially-melted and unmelted feed materials. Therefore, the CT data are presumed to be more reflective of the actual melt rate trends in continuously-fed melters than the visual data. In order to test the applicability of X-ray CT scan to the HLW glass melt rate study, several new series of HLW simulant/frit mixtures were melted in the Melt Rate Furnace (MRF) and the contents of each cooled but un-sectioned beaker were CT scanned and analyzed. For comparison purposes, a cross-sectional X-ray image of each sample was used to estimate the melt rate using the visual method. In order to see the impact of feed chemistry on melt rate more clearly, a total of ten frit-only glasses (i.e., no waste) were also made, CT scanned and analyzed. In addition, two historical glass series which were previously sectioned were re-joined and CT scanned; the results were then compared to the visual data obtained earlier. All the work performed on these historical samples will be documented separately in another report. This report describes the methodologies used to interpret and apply the results of X-ray CT scans to the HLW melt rate study and further highlights some of the key results on the compositional dependence of melt rate and the cross-comparison of the visual and CT results.

36 MATERIALS SCIENCE↗

Robotic Solutions for Remote Access and Retrieval of High-Level Radioactive Waste - 19544

This paper describes the ongoing development of robotic solutions for accessing and retrieving high-level radioactive waste from underground storage bins as part of the Calcine Retrieval Project at the INL Site. The waste is in the form of a solid powder, referred to as calcine, stored in a set of stainless steel bins within an underground concrete vault. Due to the radiation field produced by the calcine, all operations must be performed remotely. The Calcine Retrieval Project is currently carrying out proof-of-concept testing of methods for the various stages of calcine retrieval. The bins were designed with no means for access, so retrieval operations will require welding access riser pipes to the bins, followed by cutting through the bin walls from within the risers. These tasks are complicated by the fact that four of the risers must be placed off center on a domed surface, resulting in a weld joint that is curved and tilted relative to the riser axis. The Access Riser Connection robot is being developed to perform these operations using interchangeable welding and plasma cutting attachments. The majority of the calcine will be removed using a vacuum system and pneumatically transferred to storage. This system is not described in this paper. However, the bins contain several internal features that are expected to retain calcine, most notably circumferential stiffening rings on the walls and radial ribs on the floors. One of the solutions being developed for the task of retrieving this residual calcine is a vacuum crawler, a wheeled robot using vacuum to adhere to the interior walls of the bins. The vacuum crawler would use a separate vacuum system to remove residual calcine or would use compressed air to move calcine to a location from which it can be retrieved more easily. While comparable welding and wall-climbing robots have been developed before, this particular application has several constraints that are not satisfied by existing systems. For this reason, both the access riser welder and the vacuum crawler, although still under development, may be of interest to other projects faced with similar constraints. (author)

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Nonlinear Logistic Regression Mixture Experiment Modeling for Binary Data Using Dimensionally Reduced Components

This article presents and illustrates an approach using nonlinear logistic regression for modeling binary response data from a mixture experiment when the components can be partitioned into groups used to form dimensionally-reduced pseudocomponents (DRPs). A DRP is a linear combination of the components in a group, where the linear combinations over all groups are normalized so that the DRP proportions sum to unity. Nonlinear logistic regression is required because, after normalization of the linear combinations, the model expressed in terms of the DRPs is nonlinear in the parameters that specify the linear combinations. A method for obtaining nonparametric tolerance limits on the probability of a “success” for the binary response variable using a bootstrap approach is also presented. Having three DRPs enables viewing data and modeling results on a ternary plot even though there may be many more than three mixture components. A real database, involving whether or not nepheline crystals form in simulated nuclear waste glass after cooling, is used to illustrate the nonlinear logistic regression modeling and nonparametric tolerance limit approaches when there are three DRPs.

Waste glass, Nepheline, Mixture experiment, Logist↗

Energy Harvesting from Pipeline Vibration: CRADA Final Report

Investigating the extraction of energy from pipeline vibrations related to operations in the oil and gas industry. The wasted energy in the form of mechanical vibrations can be exploited to generate useful energy for low and medium power electronic devices (e.g., sensors) operating independently in deep sea and surface environments. Existing energy harvesting technologies and literature were surveyed to come up with a feasible design employing piezoelectric material. The project was important to reduce energy wastage and hence to national energy security.

30 DIRECT ENERGY CONVERSION↗

Optimization Efforts at DWPF to Ensure Waste Tank Closure by 2037 – 24404

At the Savannah River Site (SRS) in Aiken, South Carolina, the Defense Waste Processing Facility (DWPF) produces a glass-form product by processing high-level liquid waste (HLW) with borosilicate glass in a high-heated Melter, then putting the vitrified waste into stainless-steel canisters. Since 1996, DWPF has performed this vitrification process for the liquid waste mission at the SRS; the overall objective for this mission is to reduce the volume in the upstream waste tanks, so those tanks can be emptied and operationally closed. This mission seeks to eliminate the single biggest environmental risk in the state of South Carolina, which requires a robust processing strategy within the DWPF, along with optimal interface between the other facilities in the liquid waste organization (LWO). As of the end of July 2023, DWPF has safely remediated 63.7 MCi of HLW, and filled 4,319 canisters (We project that about 4,000 more canisters are needed to be filled to reach the closure goal.)

Armstead, III, Frank L.↗

Site dependent factors affecting the economic feasibility of solar powered absorption cooling

A procedure was developed to evaluate the cost effectiveness of combining an absorption cycle chiller with a solar energy system. A basic assumption of the procedure is that a solar energy system exists for meeting the heating load of the building, and that the building must be cooled. The decision to be made is to either cool the building with a conventional vapor compression cycle chiller or to use the existing solar energy system to provide a heat input to the absorption chiller. Two methods of meeting the cooling load not supplied by solar energy were considered. In the first method, heat is supplied to the absorption chiller by a boiler using fossil fuel. In the second method, the load not met by solar energy is net by a conventional vapor compression chiller. In addition, the procedure can consider waste heat as another form of auxiliary energy. Commercial applications of solar cooling with an absorption chiller were found to be more cost effective than the residential applications. In general, it was found that the larger the chiller, the more economically feasible it would be. Also, it was found that a conventional vapor compression chiller is a viable alternative for the auxiliary cooling source, especially for the larger chillers. The results of the analysis gives a relative rating of the sites considered as to their economic feasibility of solar cooling.

Bartlett, J. C.↗

The study of integrated coal-gasifier molten carbonate fuel cell systems

A novel integration concept for a coal-fueled coal gasifier-molten carbonate fuel cell power plant was studied. Effort focused on determining the efficiency potential of the concept, design, and development requirements of the processes in order to achieve the efficiency. The concept incorporates a methane producing catalytic gasifier of the type previously under development by Exxon Research and Development Corp., a reforming molten carbonate fuel cell power section of the type currently under development by United Technologies Corp., and a gasifier-fuel cell recycle loop. The concept utilizes the fuel cell waste heat, in the form of hydrogen and carbon monoxide, to generate additional fuel in the coal gasifier, thereby eliminating the use of both an O2 plant and a stream bottoming cycle from the power plant. The concept has the potential for achieving coal-pile-to-busbar efficiencies of 50-59%, depending on the process configuration and degree of process configuration and degree of process development requirements. This is significantly higher than any previously reported gasifier-molten carbonate fuel cell system.

Source record↗

Regional variations in the stability and diffusion of water-ice in the Martian regolith

Geologic evidence suggests subsurface water-ice has played an important role in the formation of Martian landforms. Forms of mass-wasting such as debris aprons and flow patterns on valley floors suggest creep deformation of ice-laden soil, while thermokarst and chaotic terrain suggest once extensive deposits of ground ice that were later removed. The global distribution of ice-related morphology was mapped. The mapping showed regional variation, in both latitude and longitude, in the distribution of debris aprons, concentric fill craters, and 'softened' crater profiles.

Mellon, Michael T.↗

Potential MER Landing Site in Melas Chasma

We have selected one area in Valles Marineris as a potential landing site for the Mars Exploration Rover (MER) mission. After 30 years of analyses, the formation of the Valles Marineris system of troughs and its associated deposits still remains an enigma. Understanding all aspects of the Valles Marineris would significantly contribute to deciphering the internal and external history of Mars. A landing site within Melas Chasma could provide insight into both the formation of Valles Marineris and the composition and origin of the interior layered deposits (ILDs). The ILDs have been proposed as: (1) sedimentary deposits formed in lakes mass wasted material from the walls; (3) remnants of the wall rock; (4) carbonate deposits; (5) aeolian deposits; and (6) volcanic. More recently, Malin and Edgett suggest that the fine-scale, rhythmic layering seen in the interior deposits, as well as other layered deposits in craters, supports a sedimentary origin. Because an understanding of the formation of Valles Marineris and its interior deposits is so important to deciphering the history of Mars, we have proposed a landing site for the MER mission on an exposure of interior deposits in western Melas Chasma. Either MER-A and MER-B could land at this same location.

Weitz, C. M.↗