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At least 19 records

Report on Fuel Cycle Facility Requirements for Deployment of Demonstration Reactors and Potential Evolutionary Fuel Cycle Scenarios

A series of fuel cycle scenarios studies were performed to inform on fuel cycle capacities and facilities needed for large-scale deployment of the Advanced Reactor Demonstration Program (ARDP) reactors and potential future evolutionary fuel cycle scenarios. The reactor deployment and evolutionary fuel cycle scenarios from the present to 2100 were developed based on the following assumptions: 1) achievement of a net-zero emissions economy in the United States by 2050, which requires a nuclear energy generation capacity of ~250 GWe by 2050, 2) the U.S. economic growth of 1% per year from 2051 to 2100, which results in ~340 GWe of nuclear energy capacity in 2100, and 3) commercial-scale recycling and high burnup fuel technologies are available after 2050. Thus, evolutionary fuel cycles with those advanced nuclear technologies start after 2050. A single once-through fuel cycle scenario was assumed from the present to 2050 to achieve a net-zero emissions economy in the United States, and the following four evolutionary fuel cycle scenarios from 2051 to 2100 were considered, 1) Once through fuel cycle with ARDP reactors (Natrium and Xe-100), 2) Once-through fuel cycle with Breed-and-Burn (B&B) fast reactors, 3) Recycling fuel cycle of used metallic fuel in fast reactors, and 4) Recycle fuel cycle of both used uranium oxide and metallic fuels in fast reactors. The projected front-end and back-end fuel cycle capacity demands are compared with the current domestic and global (if needed) fuel cycle capacities.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

An Open-Source Coupling for Depletion During Fuel Cycle Modeling

Fuel depletion is an important aspect of fuel cycle modeling, allowing a user to account for how loaded fuel compositions affect in-core and spent fuel compositions and their related fuel cycle metrics. Therefore, multiple methods have been developed to account for depletion within fuel cycle simulations. This work adds to that list of methods by introducing an open-source coupling between C$\scriptsize{YCLUS}$ and OpenMC to perform fuel depletion during a fuel cycle simulation, called OpenMCyclus. This work explains the methodology of OpenMCyclus and presents a benchmark comparison between the performance of OpenMCyclus and another C$\scriptsize{YCLUS}$ archetype that uses recipes to define spent fuel compositions. In conclusion, the development of this coupling expands the functionalities possible through C$\scriptsize{YCLUS}$ by providing real-time fuel depletion that is reactor agnostic and open source.

C$\scriptsize{YCLUS}$↗

Safeguards Challenges and Safeguards Technology Needs Assessment for Leading Thorium Fuel Cycles

Several thorium fuel cycle variants are currently being actively pursued by the global nuclear energy community. These variants have short-, medium-, and long-term deployment pathways in a variety of reactor types, including thorium-fueled molten salt reactors. Those pathways in turn give rise to a variety of fuel designs, fuel cycle facilities, and nuclear material processing requirements. These emerging fuel cycles will impact the technical implementation of safeguards, and they already raise questions about the applicability of current verification technologies. To address this issue, research is being performed to produce a detailed safeguards technology road map. It will include a needs assessment of the detection research and development (R&D;) necessary to transition the current safeguards technology toolkit to meet the verification needs of thorium fuel cycles, and to formulate the scientific basis for building new instrumentation to fill any potential capability gaps. The purpose of this technology road map is to define and inform on the safeguards technology needs for thorium fuel cycles, reflecting only the leading candidate thorium fuel cycles prioritized based on implementation timescales and the current direction of international programs. This work provides a guide to the priorities for future directed R&D; needed to bring the technology readiness levels (TRLs) of safeguards detection solutions in line with the higher TRLs of the most promising thorium fuel cycles. Herein, a summary is presented of thorium fuel cycle options and activities currently under way worldwide, which provides the technical basis for the needs evaluation. The key synergies and differences between these fuel cycles and current conventional uranium- and plutonium-based fuel cycles will be discussed from a nuclear material accountancy and detection standpoint. Reactor inventory calculations, fuel cycle simulations, and conclusions from the safeguards technology needs assessment will be presented, together with plans for experimental validation.

Worrall, Louise G.↗

Fuel Cycle Considerations for Uranium, Plutonium and Minor Actinide Partitioning and Transmutation

This paper is written in memorial of the authors' past collaborations with Max Salvatores in the area of advanced nuclear fuel cycle evaluation. In this regard, a summary is provided of the results from two international studies led by Max Salvatores in which the authors participated: (1) the expert group on Homogeneous versus Heterogeneous Recycling of Transuranics in Fast Nuclear Reactors, and (2) the expert group on Potential Benefits and Impacts of Advanced Nuclear Fuel Cycles with Actinide Partitioning and Transmutation. Both of these studies presented the authors with the opportunity to contribute the results of past and ongoing research in the U.S., facilitating engagement and discussion on these subjects with researchers from other countries and organizations, resulting in the creation of broad international views on the relative benefits and challenges of transuranic recycle (NEA, 2012a; NEA, 2012b), a testament to the leadership and capabilities of Max Salvatores. Published by Elsevier Ltd.

Taiwo, Temitope↗

Physics and technology considerations for the deuterium–tritium fuel cycle and conditions for tritium fuel self sufficiency

The tritium aspects of the DT fuel cycle embody some of the most challenging feasibility and attractiveness issues in the development of fusion systems. The review and analyses in this paper provide important information to understand and quantify these challenges and to define the phase space of plasma physics and fusion technology parameters and features that must guide a serious R&D in the world fusion program. We focus in particular on components, issues and R&D necessary to satisfy three 'principal requirements': (1) achieving tritium self-sufficiency within the fusion system, (2) providing a tritium inventory for the initial start-up of a fusion facility, and (3) managing the safety and biological hazards of tritium. A primary conclusion is that the physics and technology state-of-the-art will not enable DEMO and future power plants to satisfy these principal requirements. We quantify goals and define specific areas and ideas for physics and technology R&D to meet these requirements. A powerful fuel cycle dynamics model was developed to calculate time-dependent tritium inventories and flow rates in all parts and components of the fuel cycle for different ranges of parameters and physics and technology conditions. Dynamics modeling analyses show that the key parameters affecting tritium inventories, tritium start-up inventory, and tritium self-sufficiency are the tritium burn fraction in the plasma (f b ), fueling efficiency (η f ), processing time of plasma exhaust in the inner fuel cycle (t p ), reactor availability factor (AF), reserve time (tr) which determines the reserve tritium inventory needed in the storage system in order to keep the plant operational for time t r in case of any malfunction of any part of the tritium processing system, and the doubling time (t d ). Results show that η f f b > 2% and processing time of 1–4 h are required to achieve tritium self-sufficiency with reasonable confidence. For η f f b = 2% and processing time of 4 h, the tritium start-up inventory required for a 3 GW fusion reactor is ~11 kg, while it is <5 kg if η f f b = 5% and the processing time is 1 h. To achieve these stringent requirements, a serious R&D program in physics and technology is necessary. The EU-DEMO direct internal recycling concept that carries fuel directly from the plasma exhaust gas to the fueling systems without going through the isotope separation system reduces the overall processing time and tritium inventories and has positive effects on the required tritium breeding ratio (TBR R ). A significant finding is the strong dependence of tritium self-sufficiency on the reactor availability factor. Simulations show that tritium self-sufficiency is: impossible if AF < 10% for any η f f b , possible if AF > 30% and 1% ≤ η f f b ≤ 2%, and achievable with reasonable confidence if AF > 50% and η f f b > 2%. These results are of particular concern in light of the low availability factor predicted for the near-term plasma-based experimental facilities (e.g. FNSF, VNS, CTF), and can have repercussions on tritium economy in DEMO reactors as well, unless significant advancements in RAMI are made. There is a linear dependency between the tritium start-up inventory and the fusion power. The required tritium start-up inventory for a fusion facility of 100 MW fusion power is as small as 1 kg. Since fusion power plants will have large powers for better economics, it is important to maintain a 'reserve' tritium inventory in the tritium storage system to continue to fuel the plasma and avoid plant shutdown in case of malfunctions of some parts of the tritium processing lines. But our results show that a reserve time as short as 24 h leads to unacceptable reserve and start-up inventory requirements. Therefore, high reliability and fast maintainability of all components in the fuel cycle are necessary in order to avoid the need for storing reserve tritium inventory sufficient for continued fusion facility operation for more than a few hours. The physics aspects of plasma fueling, tritium burn fraction, and particle and power exhaust are highly interrelated and complex, and predictions for DEMO and power reactors are highly uncertain because of lack of experiments with burning plasma. Fueling by pellet injection on the high field side of tokamak has evolved to be the preferred method to fuel a burning plasma. Extrapolation from the DIII-D penetration scaling shows fueling efficiency expected in DEMO to be <25%, but such extrapolations are highly uncertain. The fueling efficiency of gas in a reactor relevant regime is expected to be extremely poor and not very useful for getting tritium into the core plasma efficiently. Gas fueling will nonetheless be useful for feedback control of the divertor operating parameters. Extensive modeling has been carried out to predict burn fraction, fueling requirements, and fueling efficiency for ITER, DEMO, and beyond. The fueling rate required to operate Q = 10 ITER plasmas in order to provide the required core fueling, helium exhaust and radiative divertor plasma conditions for acceptable divertor power loads was calculated. If this fueling is performed with a 50–50 DT mix, the tritium burn fraction in ITER would be ~0.36%, which is too low to satisfy the self-sufficiency conditions derived from the dynamics modeling for fusion reactors. Extrapolation to DEMO using this approach would also yield similarly low burn fraction. Extensive analysis presented shows that specific features of edge neutral dynamics in ITER and fusion reactors, which are different from present experiments, open possibilities for optimization of tritium fueling and thus to improve the burn fraction. Using only tritium in pellet fueling of the plasma core, and only deuterium for edge density, divertor power load and ELM control results in significant increase of the burn fraction to 1.8–3.6%. These estimates are performed with physics models whose results cannot be fully validated for ITER and DEMO plasma conditions since these cannot be achieved in present tokamak experiments. Thus, several uncertainties remain regarding particle transport and scenario requirements in ITER and DEMO. The safety standard requirements for protection of the public and release guidelines for tritium have been reviewed. General safety approaches including minimizing tritium inventories, reducing tritium permeation through materials, and decontaminating material for waste disposal have been suggested.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Reactor and fuel cycle performance of light water reactor fuel with 235 U enrichments above 5%

Recent advances in nuclear fuel materials research, particularly on the topic of accident-tolerant fuels, have brought up potential opportunities for expanding the operating envelope of existing light water reactors. As many of the performance improvements offered by these technologies may be most fully realized by increasing fuel enrichment beyond the standard 5% limit, this paper examines the potential reactor performance and fuel cycle performance of low-enriched uranium oxide fueled light water reactors by generically considering pressurized water reactors with 235 U enrichment from 5 to 7%. Advanced cladding, including accident-tolerant cladding, has the potential to increase fuel burnup limits related to hydrogen in the cladding that coincide with those limits associated with end-of-life reactivity. Therefore, higher enrichment will be necessary in order to realize the higher fuel burnups. This work includes evaluation of the fuel cycle length, discharge burnup, reactivity coefficients, and fuel cycle performance, including radioactive waste and environmental impact metrics per unit energy generated. The analysis was performed using the evaluation metrics from the US Department of Energy Office of Nuclear Energy Fuel Cycle Evaluation and Screening Study. The reactor performance and safety analysis show that enrichments between 5 and 7% would have similar fuel temperature and moderator temperature coefficients. However, the soluble boron coefficient would decrease in magnitude, requiring more corrosive boric acid in the coolant or other methods of reactivity control during the fuel cycle. At these higher enrichments the maximum burnup at the rim of the fuel pellet would increase by almost a factor of two, which is expected to impact the formation of high-burnup structure in the fuel and the corresponding thermo-mechanical fuel properties. The fuel cycle performance assessment shows that increasing enrichment reduces the quantity of high-level waste disposed per unit energy generated, but it increases the natural resource requirements normalized to a gigawatt-electricity-per-year basis. Another impact is the slightly higher discharge burnup, resulting in somewhat different activity levels of the spent nuclear fuel and high-level waste radioactivity at 100 and 100,000 years after fuel discharge. The environmental impacts—including land use, water use, carbon emission, and radiological exposure—are of the same magnitude per unit energy generated. Finally, however, the impacts are distributed differently. Less than 5% enrichment has marginally more impact on the back-end of the fuel cycle, and greater than 5% enrichment has marginally more impact on the front-end of the fuel cycle. Ultimately, no neutronic or reactor safety hindrances to employing light water reactor fuel with enrichments greater than 5% are identified; given the achievable reactor performance benefits with advanced fuels, further practical exploration of increased enrichment fuel is recommended.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Standardized verification of the C YCLUS fuel cycle simulator

Many nuclear fuel cycle simulators can analyze transitions from once-through to advanced nuclear fuel cycles. Verification studies compare various fuel cycle analysis tools to test agreement and identify sources of difference. A recent verification study, Feng et al. (2016) established transition scenario test case specifications and accordingly evaluated national laboratory nuclear fuel cycle simulators, DYMOND, VISION, ORION, and MARKAL. This work verifies the performance of C YCLUS , the agent-based, open-source fuel cycle simulator, using the test case specifications in Feng et. al. We report, C YCLUS demonstrates agreement with the results from the previous verification study. Minor differences reflect intentional, detailed material tracking in the C YCAMORE reactor module. These results extend the example results in Feng et al. to further enable future verification of additional nuclear fuel cycle simulation tools.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Optimally configuring a measurement system to detect diversions from a nuclear fuel cycle

The civilian nuclear fuel cycle is an industrial process that produces electrical power from the nuclear fission of uranium. Using a measurement system to accurately account for nuclear material, such as uranium, in a fuel cycle is important because of the possible loss or diversion of this potentially dangerous material. A measurement system is defined by a set of measurement methods, or “devices,” used to account for material flows and inventory values at specific locations in the fuel cycle. Here, we develop a simulation-optimization algorithm and an integer-programming model to find the best, or near-best, resource-limited measurement system with a high degree of confidence. The simulation-optimization algorithm minimizes a weighted sum of false positive and false negative diversion-detection probabilities while accounting for material quantities and measurement errors across a finite, discrete time horizon in hypothetical non-diversion and diversion contexts. In each time period, the estimated cumulative material unaccounted for is compared to a fixed or an optimized threshold value to assess if a “significant amount of material” is lost from a measurement system. The integer-programming model minimizes the population variance of the estimated material loss, i.e., material unaccounted for, in a measurement system. We analyze three potential problems in nuclear fuel cycle measurement systems: (i) given location-dependent device precisions, find the configuration of n devices at n locations ( n = 3) that gives the lowest corresponding objective values using the simulation-optimization algorithm and integer-programming model, (ii) find the location at which improving device precision reduces objective values the most using the simulation-optimization algorithm, and determine the effect of measurement frequency on measurement system configurations and objective values using the simulation-optimization algorithm. We obtain comparable results for each problem at least an order of magnitude faster than existing methods do. Using an optimized, rather than fixed, detection threshold in the simulation-optimization algorithm reduces the weighted sum of false positive and false negative probabilities.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Evaluating the Impact of Tritium Permeation Membrane Performance and Direct Internal Recycling on Fusion Fuel Cycle Efficiency Using TMAP8

An efficient fuel cycle is vital to sustainable and cost-effective energy generation in fusion systems. Since tritium is not widely available, fusion systems must breed their own tritium for sustainable fusion deuterium-tritium reactions. An inefficient fuel cycle increases the tritium inventory needed for operations, which increases costs, constraints on tritium management systems, and safety concerns. A fuel cycle model is a powerful tool for understanding tritium inventories and flow rates across all systems in the fuel cycle. By simplifying the technical details into time-dependent tritium flow rates and inventories, the model can simulate the entire fuel cycle with high computational efficiency, even for technologies that are still under development. It can therefore quantify the impact of new tritium management technologies on fuel cycle efficiency. To evaluate the impact of key components on reducing tritium inventory, we are using and expanding an existing fuel cycle models based on latest advancements in fuel cycle research. The new model integrates Tritium Permeation Membrane (TPM) and Direct Internal Recycling (DIR) to enhance tritium transport from blanket breeders and plasma exhaust. These fuel cycle models are implemented in TMAP8 (Tritium Migration Analysis Program, version 8), a MOOSE-based open-source application designed to provide cutting-edge capabilities for tritium transport and fuel cycle modeling. The study aims to demonstrate the extensibility of existing fuel cycle modeling capability in TMAP8 and to offer a proof-of-principle design for future fusion plant systems. The presentation will cover the performance of fuel cycle modeling capabilities available in TMAP8, highlight advancements in fuel cycle research, and present a sensitivity analysis of these models. The results underline potential approaches and technology solutions to lower tritium inventory requirements, highlighting their role in shaping the future of fusion energy.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Tensioned metastable fluid detector sensing technology for multifarious-multiscale applications in the nuclear fuel cycle

The nuclear fuel cycle presents formidable 10 30+ multiscale challenges for high-efficiency spectroscopic sensing of alpha-neutron-fission radiation signatures amidst extreme gamma-beta radiation backgrounds at various stages of the cycle; it involves diverse arenas ranging from continuous/pulsed power production, security/safeguards, spent fuel, environmental remediation, and personnel health-dosimetry. This paper discusses the novel tensioned metastable fluid detector (TMFD) sensor technology. It discusses the results of studies demonstrating extreme (10 4 Sv/h) gamma-beta field blind high intrinsic efficiencies (80–100%) for neutron-alpha-fission radiation spectrometric detection. Example studies discussed in this paper include Neutron detection with spectroscopy; H*10 neutron radiation dosimetry upwards from ultra-low10 −2 µSv/h levels; Air and/or liquid-borne trace (10 –3 Bq/mL) quantity, 1 keV energy resolved alpha/fission spectroscopy for Rn/Po/U/Pu/Am environmental isotope assays at 106:1 (β:α) ratios; Directional-position enabled extended standoff tracking of neutron emitting (shielded/unshielded) special nuclear materials while stationary or moving at highway speeds; and, U.S. Department of Energy nuclear complex wide nuclear waste reprocessing, criticality safety, health physics, and environmental applications.

Alpha-fission-neutron spectrometry↗

Integration of the Back End of the Nuclear Fuel Cycle

Management of spent nuclear fuel and high-level radioactive waste consists of three main phases – storage, transportation, and disposal – commonly referred to as the back end of the nuclear fuel cycle. Current practice for commercial spent nuclear fuel management in the United States (US) includes temporary storage of spent fuel in both pools and dry storage systems at operating or shutdown nuclear power plants. Storage pools are filling to their operational capacity, and management of the approximately 2,200 metric tons of spent fuel newly discharged each year requires transferring older and cooler spent fuel from pools into dry storage. Unless a repository becomes available that can accept spent fuel for permanent disposal, projections indicate that the US will have approximately 136,000 metric tons of spent fuel in dry storage systems by mid-century, when the last plants in the current reactor fleet are decommissioned. Current designs for dry storage systems rely on large multi-assembly canisters, the most common of which are so-called “dual-purpose canisters” (DPCs). DPCs are certified for both storage and transportation, but are not designed or licensed for permanent disposal. The large capacity (greater number of spent fuel assemblies) of these canisters can lead to higher canister temperatures, which can delay transportation and/or complicate disposal. This current management practice, in which the utilities continue loading an ever-increasing inventory of larger DPCs, does not emphasize integration among storage, transportation, and disposal. This lack of integration does not cause safety issues, but it does lead to a suboptimal system that increases costs, complicates storage and transportation operations, and limits options for permanent disposal. This paper describes strategies for improving integration of management practices in the US across the entire back end of the nuclear fuel cycle. The complex interactions between storage, transportation, and disposal make a single optimal solution unlikely. However, efforts to integrate various phases of nuclear waste management can have the greatest impact if they begin promptly and continue to evolve throughout the remaining life of the current fuel cycle. A key factor that influences the path forward for integration of nuclear waste management practices is the identification of the timing and location for a repository. The most cost-effective path forward would be to open a repository by mid-century with the capability to directly dispose of DPCs without repackaging the spent fuel into disposalready canisters. Options that involve repackaging of spent fuel from DPCs into disposalready canisters or that delay the repository opening significantly beyond mid-century could add 10s of billions of dollars to the total system life cycle cost.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Verifiable Fuel Cycle Simulation

The Verifiable Fuel Cycle Simulation (VISION) is a system-dynamics model of the entire nuclear fuel cycle, from mining to disposal, using user-defined deployment scenarios, fuel recipes, and recycling parameters. It is written in the PowerSim simulation environment and utilized MS Excel to manage data inputs and outputs.

Hays, RossD (0000000184587539)↗

Impacts of Fast-Spectrum Molten Salt Reactor Characteristics on Fuel Cycle Performance

The System Analysis and Integration Campaign nuclear fuel cycle evaluation and screening study was conducted to outline the potential benefits and challenges of nuclear fuel cycle options. The study identified continuous recycle in fast critical reactors as a common characteristic shared among some of the most promising future nuclear fuel cycles. This study was technology agnostic to focus on the underpinning physics that drives fuel cycle outcomes. This process used an analysis example to generate a physics-based understanding of the fuel cycle, and it yielded performance metrics over ranges rather than comparing absolute numbers. While no fast-spectrum molten salt reactor (MSR) has ever been built, several concepts exist using different fuels and carrier salts, many of which target high-burnup objectives, such as lightwater reactor nuclear waste consumption. Putting the resulting fuel cycle impacts of these reactor choices (e.g., fuel and neutron spectrum) into perspective is informative for our current understanding of a given fuel cycle’s performance, and it also demonstrates the applicability of MSRs to different fuel cycles. It has been established that in a fuel cycle transition, performance of a given fast-spectrum MSR depends in part on the initial fuel loading requirements and processing methods.

Betzler, Benjamin↗

Transitional cores and fuel cycle analyses in support of MIT reactor low enriched uranium fuel conversion

The Massachusetts Institute of Technology Reactor (MITR) is a research reactor in Cambridge, Massachusetts designed primarily for experiments using neutron beam and in-core irradiation facilities. At 6 MW, it delivers neutron flux and energy spectrum comparable to power light water reactors (LWRs) in a compact core using highly enriched uranium (HEU) fuel. In the framework of non-proliferation policy, research and test reactors have started a program to convert HEU fuel to low enriched uranium (LEU) fuel. A new type of LEU fuel based on a high density alloy of uranium and molybdenum (U-10Mo) is expected to allow conversion of U.S. high performance research reactors (USHPRRs) like the MITR. The Preliminary Safety Analysis Report (PSAR) for the MITR LEU conversion has been submitted and currently under review by the U.S. Nuclear Regulatory Commission (NRC). A transition core plan, from 22 fresh LEU fuel elements (i.e., beginning-of-life) gradually to 24 of them arranged in an equilibrium configuration, is expected to serve as an appendix chapter in the final SAR. The current study reported here presents the fuel cycle development, which eventually leads to the transition core plan. The results confirm the equilibrium state, where both the shim bank movement (i.e., core reactivity) as well as the content of fissile materials stabilize, can be achieved by fixed-pattern fuel management. Fission density has been evaluated for a number of fully discharged LEU fuel elements, using a best-estimate approach. The fuel cycle calculations also generate power profiles at each core state. A steady-state thermal-hydraulic safety analysis has thus been performed, where onset of nucleate boiling (ONB) is considered as the safety criterion. The results confirm significant margin to ONB at all analyzed transition and equilibrium fuel cycle states.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Idaho National Laboratory Fuel Cycle Science & Technology Overview

The Fuel Cycle Science & Technology Division delivers innovative leadership in the development and assessment of science and engineering-based solutions for the integrated nuclear fuel cycle, critical materials recovery, national security and space related applications through world-class staff and research capabilities.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Pertechnetate/perrhenate–capped Zr/Hf–Dihydroxide Dimers: Elucidating Zr–TcO 4 Co–Mobility in the Nuclear Fuel Cycle

Spent nuclear fuel contains heavy element fission products that must be separated for effective reprocessing for a safe and sustainable nuclear fuel cycle. 93 Zr and 99 Tc are high-yield fission products that co-transport in liquid-liquid extraction processes. Here we seek atomic-level information of this co-extraction process, as well as fundamental knowledge about Zr IV (and Hf IV ) aqueous speciation in the presence of topology-directing ligands such as pertechnetate (TcO 4 – ) and non-radioactive surrogate perrhenate (ReO 4 – ). In this context, we show that the flat tetrameric oxyhydroxyl-cluster [M IV 4 (OH) 8 (H 2 O) 16 ] 8+ (and related polymers) is dissociated by perrhenate/pertechnetate to yield isostructural dimers, M 2 (OH) 2 (XO 4 – ) 6 (H 2 O) 6 • 3H 2 O (M=Zr/Hf IV ; X=Re/Tc VII ), elucidated by single-crystal X-ray diffraction. We used these model compounds to understand the pervasive 93 Zr- 99 Tc coextraction with further speciation studies in water, nitric acid, and tetrabutylphosphate (TBP) -kerosene; where the latter two media are relevant to nuclear fuel reprocessing. SAXS (small angle X-ray scattering), compositional evaluation, and where experimentally feasible, ESI-MS (electrospray ionization mass spectrometry) showed that perrhenate/pertechnetate influence Zr/Hf IV -speciation in water. Here, in Zr-XO 4 solvent extraction studies to simulate fuel reprocessing, we provide evidence that TcO 4 – enhances extraction of Zr IV , and compositional analysis of the extracted metal-complexes (Zr-ReO 4 study) is consistent with the crystallized Zr IV 2 (OH) 2 (Re VII O 4 – ) 6 (H 2 O) 6 •dimer.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗