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Production and Transformation of Mixed-Valent Nanoparticles Generated by Fe(0) Electrocoagulation

Mixed-valent iron nanoparticles (NP) generated electrochemically by Fe(0) electrocoagulation (EC) show promise for on-demand industrial and drinking water treatment in engineered systems. This work applies multiple characterization techniques (in situ Raman spectroscopy, XRD, SEM, and cryo-TEM) to investigate the formation and persistence of magnetite and green rust (GR) NP phases produced via the Fe(0) EC process. Current density and background electrolyte composition were examined in a controlled anaerobic system to determine the initial Fe phases generated as well as transformation products with aging. Fe phases were characterized in an aerobic EC system with both simple model electrolytes and real groundwater to investigate the formation and aging of Fe phases produced in a system representing treatment of arsenic-contaminated ground waters in South Asia. Two central pathways for magnetite production via Fe(0) EC were identified: (i) as a primary product (formation within seconds when DO absent, no intermediates detected) and (ii) as a transformation product of GR (from minutes to days depending on pH, electrolyte composition, and aging conditions). Furthermore, this study provides a better understanding of the formation conditions of magnetite, GR, and ferric (oxyhydr)oxides in Fe EC, which is essential for process optimization for varying source waters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Major Achievements of the Springfields Decommissioning Program - 16512

Since the 1940's, Springfields has manufactured fuel products for the UK's nuclear power stations and for international customers. The early operations were in support of the atomic weapons program, closely followed by fuel manufacture for electricity generation via the Magnox power stations commencing in the late 1950's. In 2005, responsibility for the assets and liabilities of Springfields was transferred to the Nuclear Decommissioning Authority (NDA). A new company, Springfields Fuels Limited, was created to run the site, which was managed and operated by Westinghouse Electric UK Ltd on the NDA's behalf. On April 1, 2010, Westinghouse entered into an agreement with the NDA for a long-term lease of the Springfields site, which transferred responsibility for the commercial fuel manufacturing business and Springfields Fuels Limited to Westinghouse. Today, the main Springfields activities include: - Oxide fuels for Advanced Gas-cooled and Light Water Reactors, as well as intermediate fuel products, such as powders, granules and pellets, - Manufacture of Uranium Hexafluoride (now in Care and Maintenance), - Processing and recovery of Uranium residues, - Decommissioning and demolition of redundant plants and buildings. Some 120 plant buildings and support facilities have been successfully decommissioned and demolished in the period 1996 to date. These range from 1940's buildings, subsequently converted for nuclear fuel manufacture, together with some of the formerly sealed chemical agent manufacture and storage facilities. Decommissioning of the now redundant Magnox manufacturing facilities is ongoing at Springfields without compromising the other site operations. Westinghouse is managing all activities related to the whole lifecycle, planning, design, safety case, radiation protection, Post Operational Clean Out (POCO), service diversions, characterization, decommissioning all phases through to ground remediation, waste disposal and agreed end states. Decommissioning of process plants starts with the removal of the majority of radiological activity or hazard contained within the plant. This is known as Post Operational Clean Out. Once this is complete, the plant may be dismantled. Work is scoped and defined within packages (at plant or cell level) to aid control and commercial monitoring as the decommissioning is progressed. This package approach also enables clean or lightly contaminated items to be removed separately to aid potential re-cycling and minimize decontamination and waste disposal costs. Westinghouse is further optimising work package delivery by planning parallel POCO and Decommissioning work phases within plant at a cell level to systematically remove redundant plant and reduce hazard earlier, whilst optimising use of both internal and external resources to reduce total project cost. Waste and Residues from all phases are disposed of via authorized disposal routes and in accordance with our environmental authorizations. On completion of decommissioning and removal of plant and equipment the building is re-assessed radiologically, categorized and appropriate remediation work progressed to render it safe for conventional demolition. The major elements of the success achieved to date can be attributed to the following elements: - Overall programme management with extensive experience of planning, cost, and risk management. Integration of the programme within a major commercial site without compromising safety or operations. - Complete site EHS management working within a complex regulatory framework including the Nuclear Site Licenses, Environmental Authorisations and Security requirements. - Avoiding safety complacency by use of rigorous and systematic process to emphasise safety over competing goals. Including structured use of Human Performance and Corrective Action and Learning processes. - Unique safety experiences attained through complex hazard reduction across a broad range of uranium manufacturing and chemical hazard/agent facilities. - Project leadership and excellence utilizing a core site team to deploy repeatable processes and safe practices to deliver complex scope within budget and schedule. - Optimised use of internal and external resources, with extensive use of Operating Experience to drive continuous improvement and problem resolution. - Management of Contractors from initial selection, pre-qualification, tender assessment and Performance using varied contract forms across delivery phases. - Use of Westinghouse expertise for safety case, waste management, uranium recovery, health physics and design. - Implementation of a work package to ensure gated discreet manageable packages. Underpinned by package specific method statements, with appropriate hold points to maintain management and control of the works. - Continuous local safety focus via safety planning, induction, plant specific training, proactive risk assessment, and a defined approach to decoupling operating plant safety cases enabling focussed and usable documentation. This paper will provide an overview of the latest decommissioning activities achieved on the Springfields site and will focus on best practices that allowed Westinghouse to maintain the program on time and on budget. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Application of Modular Design in Abatement of Fuel Element Debris (FED) Liquid Waste Stream - 16635

This paper provides a description of the processes applied within the Aqueous Discharge Abatement Plant (ADAP) at Bradwell nuclear power plant in the UK. This incorporates the Fuel Element Debris (FED) abatement plant and the Modular Active Effluent Treatment Plant (MAETP). These plants are housed in adjacent, but separate, structures and are inter-linked and share common services and control systems. The FED abatement plant, which has a shorter mission than MAETP, can be removed for decommissioning or redeployment without any impact to MAETP operation. ADAP treats aqueous waste streams generated during the ongoing decontamination and decommissioning (D and D) operations for release from the Bradwell Power Station. The plant is designed to receive and treat two major classes of liquids: 1. Slightly contaminated water from various D and D sources and collected rainwater from the power station, referred to as Aqueous Effluent (AE). 2. Dissolved fuel element debris solution. This comprises of contaminated magnesium alloy (generated during the stripping of external structures from spent Magnox fuel elements prior to shipment for reprocessing) which has been dissolved in nitric acid. All received wastes are treated to remove heavy metals and radioactive constituents prior to isolation, sampling, verification, and ultimately release to the Blackwater Estuary. The treatment consists of multiple processes including precipitation, filtration, adsorption and ion exchange carefully designed to remove targeted radionuclides and heavy metals. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Right-Sized Reuse - Use a Systematic Process, and Design for a Specialized, Yet Flexible Result - 13558

The process of transferring real property from the U.S. Department of Energy (DOE) is always the same - except when it's not. The most frequently asked questions in the process are: how can this take so long and be so complex, and why is it different every time? The process of transferring real property from the Department of Energy is always the same - except when it's not. Repeat as needed. The authority for DOE to transfer property is found in the Atomic Energy Act of 1954 (AEA). Specifically, the transfer of real property for mission-related purposes is done pursuant to the AEA Section 161(g). Another rule that can provide certain unique benefits to the transferee is found in 10 Code of Federal Regulations (CFR) Part 770, Transfer of Real Property at Defense Nuclear Facilities for Economic Development; it can be followed for economic development purposes at defense nuclear facilities. All federal real property transfers include at minimum a National Environmental Policy Act (NEPA) review and a Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) chap. 120(h) environmental due diligence evaluation. The end-point objective is to be able to demonstrate that a transfer is protective of human health and the environment - typically attained via a risk evaluation. That's it...mostly. None of these requirements are new; their processes are well-known. So, why is it different every time there is a transfer and what can be done to move things along? Time and the perception of open-ended schedules kill projects. Economic development projects that are proposed by Community Reuse Organizations (CROs) and others or by parties who need private capital are especially time-sensitive. It is not reasonable to expect business interests or investors to wait two years while the property transfer process is carried out. Lenders are also risk-sensitive and not solely business-risk sensitive. After all, these are federal properties where contamination is a factor. What are some of the things you can do to address those time and risk issues? Issues of time and complexity arise from several variables. Short-sighted vision and lack of project definition lead to wasted effort and lengthy delays. Some variability on the input side of the process can be controlled in a way that will save you time and actually work to your advantage. Steps can be taken to systematize the transfer process on the agency's part and on the requester/grantee's part. Having the right mix of dedicated people from the beginning, planning with flexibility, coordinating with the clean-up program at your site, knowing the interests and issues of your stakeholders, and working with the CRO/economic development authorities - all of these measures and others can and will help you. The key is not simply knowing the steps and making a punch-list, but understanding the steps and how to work with and use them. These concepts can be applied to create a vision of success for those engaged in real property transfer. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Using Department of Energy (DOE) Order 435.1 To Find a Cost Effective Waste Management Option. - 12241

The Depleted Uranium Hexafluoride Project in Portsmouth Ohio was faced with an interesting dilemma. During hot functional testing in August 2010, an upset condition caused gaseous depleted uranium hexafluoride (UF{sub 6}) to come in contact with the hydrofluoric acid (HF) vapor stream. Although the resulting uranium contamination found in the condensed aqueous hydrofluoric acid was very low, it exceeded the Department of Energy (DOE) authorized release limit. After evaluating several commercial options for treatment and disposal using the guidelines found in DOE Order 435.1, Waste Control Specialists LLC was selected for the treatment of the waste, with EnergySolutions' Clive facility selected for disposal of the treated residues. The waste was safely transported from Piketon, Ohio to Andrews, Texas, where it was treated to meet the land Disposal Restrictions (LDR), and was disposed in EnergySolutions operational mixed waste cell. The entire effort was interesting for several reasons. The waste was generated during the last year of the first Depleted Uranium Hexafluoride contractor. The waste became additional scope for the new contractor, adding time delays and introducing new personnel into the project. The effort was also unique because it demonstrated the process mandated by DOE Order 435.1 to evaluate all options, including commercial options, could reveal solutions to waste management problems that are currently available and more cost effective, but not well know within the DOE complex. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Methods to estimate the transfer of contaminants into recycling products – A case study from Austria

Highlights: • Recycling of waste materials includes the risk of recycling hazardous substances. • Comparison of contaminants in recycling products to primary products and check of compliance with limit values. • Evaluation matrix to quickly scan the environmental and health risks of wastes for recycling. • Optimised sorting and quality control systems prevent transfer of contaminants into product cycles. - Abstract: Recycling of waste materials is desirable to reduce the consumption of limited primary resources, but also includes the risk of recycling unwanted, hazardous substances. In Austria, the legal framework demands secondary products must not present a higher risk than comparable products derived from primary resources. However, the act provides no definition on how to assess this risk potential. This paper describes the development of different quantitative and qualitative methods to estimate the transfer of contaminants in recycling processes. The quantitative methods comprise the comparison of concentrations of harmful substances in recycling products to corresponding primary products and to existing limit values. The developed evaluation matrix, which considers further aspects, allows for the assessment of the qualitative risk potential. The results show that, depending on the assessed waste fraction, particular contaminants can be critical. Their concentrations were higher than in comparable primary materials and did not comply with existing limit values. On the other hand, the results show that a long-term, well-established quality control system can assure compliance with the limit values. The results of the qualitative assessment obtained with the evaluation matrix support the results of the quantitative assessment. Therefore, the evaluation matrix can be suitable to quickly screen waste streams used for recycling to estimate their potential environmental and health risks. To prevent the transfer of contaminants into product cycles, improved data of relevant substances in secondary resources are necessary. In addition, regulations for material recycling are required to assure adequate quality control measures, including limit values.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Processing and properties of a solid energy fuel from municipal solid waste (MSW) and recycled plastics

Highlights: • Briquetting was used to produce solid fuels from municipal solid waste and recycled plastics. • Optimal drying, processing temperature and pressure were found to produce stable briquettes. • Addition of waste plastics yielded heating values comparable with typical coal feedstocks. • This processing method improves utilization of paper and plastic diverted from landfills. - Abstract: Diversion of waste streams such as plastics, woods, papers and other solid trash from municipal landfills and extraction of useful materials from landfills is an area of increasing interest especially in densely populated areas. One promising technology for recycling municipal solid waste (MSW) is to burn the high-energy-content components in standard coal power plant. This research aims to reform wastes into briquettes that are compatible with typical coal combustion processes. In order to comply with the standards of coal-fired power plants, the feedstock must be mechanically robust, free of hazardous contaminants, and moisture resistant, while retaining high fuel value. This study aims to investigate the effects of processing conditions and added recyclable plastics on the properties of MSW solid fuels. A well-sorted waste stream high in paper and fiber content was combined with controlled levels of recyclable plastics PE, PP, PET and PS and formed into briquettes using a compression molding technique. The effect of added plastics and moisture content on binding attraction and energy efficiency were investigated. The stability of the briquettes to moisture exposure, the fuel composition by proximate analysis, briquette mechanical strength, and burning efficiency were evaluated. It was found that high processing temperature ensures better properties of the product addition of milled mixed plastic waste leads to better encapsulation as well as to greater calorific value. Also some moisture removal (but not complete) improves the compacting process and results in higher heating value. Analysis of the post-processing water uptake and compressive strength showed a correlation between density and stability to both mechanical stress and humid environment. Proximate analysis indicated heating values comparable to coal. The results showed that mechanical and moisture uptake stability were improved when the moisture and air contents were optimized. Moreover, the briquette sample composition was similar to biomass fuels but had significant advantages due to addition of waste plastics that have high energy content compared to other waste types. Addition of PP and HDPE presented better benefits than addition of PET due to lower softening temperature and lower oxygen content. It should be noted that while harmful emissions such as dioxins, furans and mercury can result from burning plastics, WTE facilities have been able to control these emissions to meet US EPA standards. This research provides a drop-in coal replacement that reduces demand on landfill space and replaces a significant fraction of fossil-derived fuel with a renewable alternative.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mineral reaction kinetics constrain the length scale of rock matrix diffusion

Mass transport by aqueous fluids is a dynamic process in shallow crustal systems, redistributing nutrients as well as contaminants. Rock matrix diffusion into fractures (void space) within crystalline rock has been postulated to play an important role in the transient storage of solutes. The reacted volume of host rock involved, however, will be controlled by fluid-rock reactions. Here we present the results of a study which focusses on defining the length scale over which rock matrix diffusion operates within crystalline rock over timescales that are relevant to safety assessment of radioactive and other long-lived wastes. Through detailed chemical and structural analysis of natural specimens sampled at depth from an active system (Toki Granite, Japan), we show that, contrary to commonly proposed models, the length scale of rock matrix diffusion may be extremely small, on the order of centimetres, even over timescales of millions of years. This implies that in many cases the importance of rock matrix diffusion will be minimal. Additional analyses of a contrasting crystalline rock system (Carnmenellis Granite, UK) corroborate these results.

58 GEOSCIENCES↗

Vertical Extraction Process Implemented at the 118-K-1 Burial Ground for Removal of Irradiated Reactor Debris from Silo Structures - 12431

The primary objective of a remediation project is the safe extraction and disposition of diverse waste forms and materials. Remediation of a solid waste burial ground containing reactor hardware and irradiated debris involves handling waste with the potential to expose workers to significantly elevated dose rates. Therefore, a major challenge confronted by any remediation project is developing work processes that facilitate compliant waste management practices while at the same time implementing controls to protect personnel. Traditional burial ground remediation is accomplished using standard excavators to remove materials from trenches and other excavation configurations often times with minimal knowledge of waste that will be encountered at a specific location. In the case of the 118-K-1 burial ground the isotopic activity postulated in historic documents to be contained in vertical cylindrical silos was sufficient to create the potential for a significant radiation hazard to project personnel. Additionally, certain reported waste forms posed an unacceptably high potential to contaminate the surrounding environment and/or workers. Based on process knowledge, waste management requirements, historic document review, and a lack of characterization data it was determined that traditional excavation techniques applied to remediation of vertical silos would expose workers to unacceptable risk. The challenging task for the 118-K-1 burial ground remediation project team then became defining an acceptable replacement technology or modification of an existing technology to complete the silo remediation. Early characterization data provided a good tool for evaluating the location of potential high exposure rate items in the silos. Quantitative characterization was a different case and proved difficult because of the large diameter of the silos and the potential for variable density of attenuating soils and waste forms in the silo. Consequently, the most relevant information supporting job planning and understanding of the conditions was the data obtained from the gross gamma meter that was inserted into each casing to provide a rough estimate of dose rates in the tubes. No added value was realized in attempting to quantify the source term and/or associate the isotopic activity with a particular actual waste form (e.g., sludge). Implementing the WRM system allowed monitoring of worker and boundary exposure rates from a distance, maintaining compliance with ALARA principles. This system also provided the project team early knowledge of items being removed that had high exposure rates associated with them, thus creating an efficient method of acknowledging an issue and arriving at a solution prior to having an upset condition. An electronic dosimeter with telemetry capability replaced the excavator mounted AMP-100 system approximately half way through remediation of the silos. Much higher connectivity efficiency was derived from this configuration. Increasing the data feed efficiency additionally led to less interruption of the remediation effort. Early in system testing process a process handicap on the excavator operator was acknowledged. A loss of depth perception resulted when maneuvering the excavator and bucket using the camera feed to an in-cab monitor. Considerable practice and mock-up testing allowed this handicap to be overcome. The most significant equipment failures involved the cable connection to the camera mounted between the clamshell bucket jaws and the video splitter in the excavator cab. Rotation of the clamshell bucket was identified as the cause of cable connection failures because of the cyclic twisting motion and continuous mechanical jarring of the connection. In-cab vibration was identified as the culprit in causing connection failures of the video splitter. While these failures were repaired, substantial production time was lost. Ultimately, the decision was made to purchase a second cable and higher quality video splitter eliminate the down time. An engineering improvement for future operations would be inserting cable pig tails at more stressed cable connection points to facilitate rapid change out of the cable should that be required. Overall, the system performed better than expected in a safe and efficient manner. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

When Spreadsheets Become Software - Quality Control Challenges and Approaches - 13360

As part of a preliminary waste acceptance criteria (PWAC) development, several commercial models were employed, including the Hydrologic Evaluation of Landfill Performance model (HELP) [1], the Disposal Unit Source Term - Multiple Species model (DUSTMS) [2], and the Analytical Transient One, Two, and Three-Dimensional model (AT123D) [3]. The results of these models were post-processed in MS Excel spreadsheets to convert the model results to alternate units, compare the groundwater concentrations to the groundwater concentration thresholds, and then to adjust the waste contaminant masses (based on average concentration over the waste volume) as needed in an attempt to achieve groundwater concentrations at the limiting point of assessment that would meet the compliance concentrations while maximizing the potential use of the landfill (i.e., maximizing the volume of projected waste being generated that could be placed in the landfill). During the course of the PWAC calculation development, one of the Microsoft (MS) Excel spreadsheets used to post-process the results of the commercial model packages grew to include more than 575,000 formulas across 18 worksheets. This spreadsheet was used to assess six base scenarios as well as nine uncertainty/sensitivity scenarios. The complexity of the spreadsheet resulted in the need for a rigorous quality control (QC) procedure to verify data entry and confirm the accuracy of formulas. (authors)

54 ENVIRONMENTAL SCIENCES↗

Evaluation of Mineral Deposits Along the Little Wind River, Riverton, WY, Processing Site

In 2012, the U.S.Department of Energy (DOE) began reassessing the former Riverton, Wyoming, Processing Site area for potential contaminant sources impacting groundwater. A flood in 2010 along the Little Wind River resulted in increases in groundwater contamination (DOE 2013).This investigation is a small part of continued efforts by DOE and other stakeholders to update human health and ecological risk assessments, to make a comprehensive examination of all exposure pathways to ensure that the site remains protective through established institutional controls. During field inspections at the Riverton Site in 2013, a white evaporitic mineral deposit was identified along the bank of the Little Wind River within the discharge zone of the groundwater contamination plume. In December 2013, Savannah River National Laboratory (SRNL) personnel collected a sample for analysis by X-ray fluorescence (Figure 1 shows the type of material sampled). The sample had a uranium concentration of approximately 64 to 73 parts per million. Although the uranium in this mineral deposit is within the expected range for evaporatic minerals in the western United States (SRNL 2014), DOE determined that additional assessment of the mineral deposit was warranted. In response to the initial collection and analysis of a sample of the mineral deposit, DOE developed a work plan (Work Plan to Sample Mineral Deposits Along the Little Wind River, Riverton, Wyoming, Processing Site [DOE 2014]) to further define the extent of these mineral deposits and the concentration of the associated contaminants (Appendix A). The work plan addressed field reconnaissance, mapping, sampling, and the assessment of risk associated with the mineral deposits adjacent to the Little Wind River.

54 ENVIRONMENTAL SCIENCES↗

Soil and Water Chemistry and Trace Metal Extractability and Speciation in Wetland Soils from Illinois and South Carolina and Stream Sediments from Tennessee

Dataset revised on October 15, 2021. This revision adds sulfur and iron X-ray absorption near-edge structure spectra for the wetland soils and stream sediments from the field areas. It also renames the sample locations in a way that is more intuitive to readers of the companion paper that is under review. Finally, the data filenames and organization have been updated in their labeling to parallel the data sources in the associated paper. The abstract text and methods were also revised to reflect the data that was added to the dataset.Trace metals are essential for microbially-mediated biogeochemical processes occurring in anoxic wetland soils and stream bed sediments, such as denitrification, methanogenesis, and mercury methylation. Low availability of these elements may potentially inhibit key components of anaerobic carbon and nitrogen cycling and contaminant transformation. The solid-phase speciation of trace metals likely plays an important role in controlling their bioavailability. Metal speciation is well studied in contaminated soils and sediments as well as those naturally elevated in trace metals. However, less is known regarding the chemical forms of trace metals in systems having concentrations similar to geological background levels, the very settings where metal limitations may be most prevalent. We have investigated trace metal concentrations, extractability, and solid-phase speciation in three freshwater subsurface aquatic systems: marsh wetland soils, riparian wetland soils, and the sediments of a streambed.Data are provided for marsh wetland soils at Argonne National Laboratory, riparian wetland soils in the Tims Branch watershed at Savannah River National Laboratory, and stream bed sediments from East Fork Poplar Creek near Oak Ridge National Laboratory. Soil and sediment elemental abundances, mineralogy, and extractable nutrients as well as dissolved major elements, anions, trace metals, and nutrients in the overlying surface waters are provided. In addition, the results of sequential chemical extraction for the trace metals cobalt, nickel, copper, and zinc from the soils and sediment are reported as well as X-ray absorption near-edge structure (XANES) spectra in these materials are reported. To aid interpretation of these data, XANES spectra of sulfur in the soils and sediments as well as both XANES and extended X-ray absorption fine structure (EXAFS) spectra of iron in these materials are reported. The data package also includes the XANES spectra of reference standards and a potential interferent in the measurements. All data are provided in text-based CSV format with header sections indicating the data contained in each file and the corresponding units. Note that "u" is used in place of Greek lower case mu to indicate the micro prefix on units.

54 ENVIRONMENTAL SCIENCES↗

Monitoring and flaw detection during wire-based directed energy deposition using in-situ acoustic sensing and wavelet graph signal analysis

The goal of this work is to detect flaw formation in the wire-based directed energy deposition (W-DED) process using in-situ sensor data. The W-DED studied in this work is analogous to metal inert gas electric arc welding. The adoption of W-DED in industry is limited because the process is susceptible to stochastic and environmental disturbances that cause instabilities in the electric arc, eventually leading to flaw formation, such as porosity and suboptimal geometric integrity. Moreover, due to the large size of W-DED parts, it is difficult to detect flaws post-process using non-destructive techniques, such as X-ray computed tomography. Accordingly, the objective of this work is to detect flaw formation in W-DED parts using data acquired from an acoustic (sound) sensor installed near the electric arc. To realize this objective, we develop and apply a novel wavelet integrated graph theory approach. The approach extracts a single feature called graph Laplacian Fiedler number from the noise-contaminated acoustic sensor data, which is subsequently tracked in a statistical control chart. Using this approach, the onset of various types of flaws are detected with a false alarm rate less-than 2%. This work demonstrates the potential of using advanced data analytics for in-situ monitoring of W-DED.

42 ENGINEERING↗

Hydrogen Detection Strategies to Support H2@SCALE - The NREL Sensor Laboratory

Hydrogen represents a major pathway to decarbonize and stabilize the national and international energy industry and select manufacturing markets. To facilitate the development of hydrogen markets, the US Department of Energy initiated H2@Scale to bring together stakeholders to advance affordable hydrogen production, transport, storage, and utilization to increase revenue opportunities in multiple energy sectors. One major impediment to hydrogen implementation is cost. To expedite the use of hydrogen in energy and other markets, the United States announced in 2021 the Hydrogen Shot, which seeks to reduce the cost of clean hydrogen by 80% to $1 per 1 kilogram in 1 decade ("1 1 1"). As the cost of hydrogen drops, new applications will emerge that will require unique configurations of existing equipment and infrastructure, and eventually lead to advances in the generation and utilization of hydrogen. As the hydrogen economy expands, sensors and detection methods will need to adapt to changing infrastructure demands to address the primary targets of health & safety, emissions monitoring, and process control. The NREL Sensor Laboratory is playing a pivotal role in advancing the use of hydrogen sensors and detection methodologies in each of these categories to support DOE's mission for safe and efficient utilization in emerging markets. Health & safety monitors are required to ensure that operators and facilities can react to unintended hydrogen releases, either as GH2, LH2, or as a constituent of blends (e.g., natural gas or ammonia). Current detection methodologies focus on safety applications to detect near its lower flammable limit (4 vol %), and typically include point sensors in applications such as fixed or mobile detectors (e.g., personal gas monitors). Methodologies amenable for area detection include acoustic, emerging optical imaging methods, and flame detectors. Comparable detection strategies can be utilized for emissions monitoring and quantization, however few methods can simultaneously cover both low (emissions) and high (health & safety) levels. Deployment of emission level detectors will be required to 1) reduce product loss through small but potentially significant leaks from an environmental or cost perspective, 2) reduce downtime of high demand systems by early identification of eminent system failures (leaks through pump or compressor seals indicative of impending failure), and 3) address potential emission monitoring requirements that may be set by regulating bodies. The first two points should be adopted by industry to reduce the cost-of-goods-sold. The third main category for hydrogen detection relates to process control and may be advantageous for many existing applications. Two main applications are emerging. For example, the purity requirements for hydrogen that is dispensed from refueling systems for hydrogen fuel cell electric vehicles (FCEV) is rigorously regulated by the Standard SAE J2719, which prescribes maximum allowable levels of multiple impurities in the hydrogen fuel and must be verified by a regulatory body. Hydrogen contaminant detectors (HCD) integrated to the fueling station can assure this compliance. HCDs must be able operate in 100% H2 backgrounds and be able to distinguish between multiple contaminants at low ppm to low ppb levels. Secondly, as a strategy to decarbonize the natural gas grid, there are proposals to blend hydrogen with natural gas. This blending will affect transport applications (pipeline infrastructure), stationary combustion systems (turbines), and consumer and commercial appliances. In the short-term, hydrogen levels up to 20% are proposed. Variations in the hydrogen level can have dramatic impact on the combustion process and on the potential response of safety sensors. These mixtures may be regulated so that the concentration at a delivery point must be monitored with high precision. However, routine maintenance may introduce background gases such as ambient air (with water) or maintenance gases (introduced with welding processes or adhesive outgassing.) Therefore, the detection methodology must be robust enough to recover or respond to various contaminants. Several reviews can be found in literature addressing sensing and detection technologies, including their limitations and applications. However, for most applications, limitations can be alleviated by combining various detection techniques either through system integration or implementation of machine learning methods (artificial intelligence). In this presentation, we will discuss several applications, highlight their current approach for hydrogen detection, and suggest detection strategies to supplement their limitations.

ENERGY STORAGE,HYDROGEN↗

Overview and History of DOE's Hanford Site - 12502

Hanford's DOE offices are responsible for one of the largest nuclear cleanup efforts in the world, cleaning up the legacy of nearly five decades of nuclear weapons production. Nowhere in the DOE Complex is cleanup more challenging than at the Hanford Site in southeastern Washington. Hanford cleanup entails remediation of hundreds of large complex hazardous waste sites; disposition of nine production reactors and the preservation of one as a National Historic Landmark; demolition of hundreds of contaminated facilities including five enormous process canyons; remediation of billions of gallons of contaminated groundwater; disposition of millions of tons of low-level, mixed low-level, and transuranic waste; disposition of significant quantities of special nuclear material; storage and ultimate disposition of irradiated nuclear fuel; remediation of contamination deep in the soil that could impact groundwater; decontamination and decommissioning of hundreds of buildings and structures; and treatment of 56 million gallons of radioactive waste in 177 large underground tanks through the construction of a first-of-its-kind Waste Treatment Plant. Cleanup of the Hanford Site is a complex and challenging undertaking. The DOE Richland Operations Office has a vision and a strategy for completing Hanford's cleanup including the transition to post-cleanup activities. Information on the strategy is outlined in the Hanford Site Completion Framework. The framework describes three major components of cleanup - River Corridor, Central Plateau, and Tank Waste. It provides the context for individual cleanup actions by describing the key challenges and approaches for the decisions needed to complete cleanup. The U.S. Department of Energy (DOE), as regulated by the U.S. Environmental Protection Agency (EPA) and Washington State Department of Ecology (Ecology), is implementing a strategy to achieve final cleanup decisions for the River Corridor portion of the Hanford Site. The DOE Richland Operations Office (RL) and DOE Office of River Protection (ORP) have prepared this document to describe the strategy and to begin developing the approach for making cleanup decisions for the remainder of the Hanford Site. DOE's intent is that the Completion Framework document will facilitate dialogue among the Tri-Parties and with Hanford's diverse interest groups, including Tribal Nations, State of Oregon, Hanford Advisory Board, Natural Resource Trustees, and the public. Future cleanup decisions will be enhanced by an improved understanding of the challenges facing cleanup and a common understanding of the goals and approaches for cleanup completion. The overarching goals for cleanup are sevenfold. - Goal 1: Protect the Columbia River. - Goal 2: Restore groundwater to its beneficial use to protect human health, the environment, and the Columbia River. - Goal 3: Clean up River Corridor waste sites and facilities to: Protect groundwater and the Columbia River. Shrink the active cleanup footprint to the Central Plateau, and support anticipated future uses of the land. - Goal 4: Clean up Central Plateau waste sites, tank farms, and facilities to: Protect groundwater. Minimize the footprint of areas requiring long-term waste management activities. Support anticipated future uses of the land. - Goal 5: Safely manage and transfer legacy materials scheduled for off-site disposition including special nuclear material (including plutonium), spent nuclear fuel, transuranic waste, and immobilized high-level waste. - Goal 6: Consolidate waste treatment, storage, and disposal operations on the Central Plateau. - Goal 7: Develop and implement institutional controls and long-term stewardship activities that protect human health, the environment, and Hanford's unique cultural, historical and ecological resources after cleanup activities are completed. These goals embody more than 20 years of dialogue among the Tri-Party Agencies, Tribal Nations, State of Oregon, stakeholders, and the public. They carry forward key values captured in forums such as the Hanford Future Site Uses Working Group, Tank Waste Task Force, Hanford Summits, and Hanford Advisory Board Exposure Scenario Workshops, as well as more than 200 advice letters issued by the Hanford Advisory Board (http://www.hanford.gov/page.cfm/hab). These goals help guide all aspects of Hanford Site cleanup. Cleanup activities at various areas of the site support the achievement of one or more of these goals. These goals help set priorities to apply resources and sequence cleanup efforts for the greatest benefit. These goals reflect DOE's recognition that the Columbia River is a critical resource for the people and ecology of the Pacific Northwest. The 50-mile stretch of the river known as the Hanford Reach is home to the last free-flowing section of the river in the U.S. As one of the largest rivers in North America, its waters support a multitude of uses that are vital to the economic and environmental well being of the region and it is particularly important in sustaining the culture of Native Americans. Cleanup actions must protect this river. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Decommissioning of the Hematite Former Fuel Cycle Facility using a decision flow logic based work control process

The remediation and decommissioning of the Hematite Former Fuel Cycle Facility (FFCF), the Hematite Facility, is currently being carried out by Westinghouse Electric Company LLC under the Hematite Decommissioning Project (HDP). The Hematite Facility is located near the town of Hematite, Missouri, USA. The Hematite Facility consists of 228 acres of land with primary operations historically being conducted within the central portion of the property that is roughly 10 acres including Burial Pits and the Site Pond area. Decommissioning and remediation activities are being performed with the eventual objective of the release of the property. Primary contaminants include the legacy disposal and contamination of natural and enriched uranium from the nuclear fuel cycle, as well as chemicals used during the facility operations. Two major regulatory bodies, the U.S. Nuclear Regulatory Commission (NRC) and the Missouri Department of Natural Resources (MDNR), provide critical roles in the approval and oversight of the current regulatory path to remediation, decommissioning and eventual release. Further, remediation and decommissioning activities are performed under the implementing policies, plans, and procedures under the Hematite Decommissioning Plan (DP) and the Record of Decision (ROD). Remediation and decommissioning tasks at the Hematite Former Fuel Cycle Facility, referred to as the Hematite Facility, are performed against a disciplined decision logic flow that applies accumulated technical and monitoring data to determine each step of the excavation, exhumation, and removal of wastes from the Burial Pits and the remaining Areas of Concern (AOC). Decision flow logic is based upon the nuclear criticality safety controls and threshold conditions, relative level of radioactive and chemical contamination, security protocol, and final waste stream disposition. The end result is to remediate the residual radioactive and chemical contamination to approved dose-based and risk-based cleanup criteria as negotiated with U.S. Federal and State Regulators. The purpose of the paper is to provide a summary of the successful implementation of the decision flow logic to the remediation and decommissioning tasks performed to date. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Eruptive Activity on the Western Flank of Piton de la Fournaise (La Réunion Island, Indian Ocean): Insights on Magma Transfer, Storage and Evolution at an Oceanic Volcanic Island

Abstract Petrological and geochemical (major element, trace element, Sr–Nd isotope) data for recent (<5 kyr old) basalts that sporadically erupt on the western flank of Piton de la Fournaise (PdF), one of the most active volcanoes on Earth, allow the tracking of magma transfer and evolution from mantle to crustal depths. In the western peripheral area of PdF we document the broadly synchronous eruptions of (1) primitive olivine and olivine–clinopyroxene transitional basalts with tholeiitic affinity that are closely associated in space with (2) transitional olivine basalts with alkaline affinity, and (3) hybrid lavas, intermediate between the ‘alkaline’ and the ‘tholeiitic’ end-members. The composition of the latter overlaps with that of the lavas frequently erupted from the conduit system feeding the main summit cone. AlphaMELTS modelling, and fluid inclusion and clinopyroxene barometry, constrain the conditions of magma storage at 10–30 km, and the ascent of magma from the upper mantle to the shallow crustal plumbing system. Variable degrees of mantle melting, together with minor source heterogeneity and contamination with cumulate-derived partial melts, contribute to the diversity of PdF magmas. However, all these processes do not represent the dominant factors that produce the large variability we found in major element composition. Indeed, the composition of basalts erupted from PdF peripheral centers is strongly controlled by polybaric olivine–clinopyroxene fractionation at pressures higher than 3 kbar. Crystal textures and geochemical modelling suggest that fast magma ascent is critical to prevent clinopyroxene dissolution. Conversely, long-lasting magma stagnation promotes pyroxene resorption and magma differentiation. ‘Central’ eruptions occurring close to the PdF summit cone emit variably more evolved melts, which result from olivine–clinopyroxene–plagioclase differentiation at intermediate–shallow pressure (<3 kbar and in most cases <1 kbar). Deep and extensive magma mixing before injection into the crustal magma conduit system, located below the summit region, results in the apparent homogeneity of basalts erupted from the central area. As regards ‘peripheral’ eruptions, deep-seated stagnation of basaltic melts and differentiation at the mantle–crust transition zone (c. 4 kbar) produces a range of magma compositions. We demonstrate that rapid magma ascent from deep-seated reservoirs can bypass the central plumbing system. The eruptions of these magmas both in the central area and on the densely populated flanks have major consequences in terms of volcanic hazard at PdF.

Boudoire, G.↗