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At least 1,063 records · Page 59

Milestone Report - M3FT-15OR03120213 - A Literature Survey to Identify Potentially Problematic Volatile Iodine-Bearing Species Present in Off-Gas Streams

Four radionuclides have been identified as being sufficiently volatile in the reprocessing of nuclear fuel that their gaseous release needs to be controlled to meet U.S. regulatory requirements (Jubin et al. 2011, 2012). These radionuclides are 3 H, 14 C, 85 Kr, and 129 I. Of these, 129 I has the longest half-life and potentially highest biological impact. Accordingly, control of the release of 129 I is most critical with respect to U.S. regulations for the release of radioactive material in stack emissions. Current U.S. Environmental Protection Agency regulation governing nuclear facilities (40 CFR 190) states that the total quantity of radioactive materials entering the general environment from the entire uranium fuel cycle, per gigawatt-year of electrical energy produced by the fuel cycle, must contain less than 5 mCi of 129 I. The study of inorganic iodide in off-gas systems has been almost exclusively limited to I 2 , and the focus of organic iodide studies has been CH 3 I.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Performance evaluation of the ORNL multi-elemental XRF analysis algorithms

Hybrid K-Edge Densitometer (HKED) systems integrate both K-Edge Densitometry (KED) and X-Ray Fluorescence (XRF) analyses to provide accurate rapid, assay results of the uranium and plutonium content of dissolver solution samples from nuclear fuel reprocessing facilities. Introduced for international safeguards applications in the late 1980s, the XRF component of the hybrid analyses is limited to quantification of U and Pu over a narrow range of U:Pu concentration ratios in the vicinity of ≈100. The analysis was further limited regarding the presence of minor actinide components where only a single minor actinide (typically Am) is included in the analysis and then only treated as an interference. The evolving nuclear fuel cycle has created the need to assay more complex dissolver solutions where uranium may no longer be the dominant actinide in the solution and the concentrations of the so called minor actinides (e.g., Th, Np, Am, and Cm) are sufficiently high that they can no longer be treated as impurities and ignored. Extension of the traditional HKED Region of Interest (ROI) based analysis to include these additional actinides is not possible due to the increased complexity of the XRF spectra. Oak Ridge National Laboratory (ORNL) has developed a spectral fitting approach to the HKED XRF measurement with an enhanced algorithm set to accommodate these complex XRF spectra. This report provides a summary of the spectral fitting methodology and examines the performance of these algorithms using data obtained from the ORNL HKED system, as well as data provided by the International Atomic Energy Agency (IAEA) on actual dissolver solutions.

97 MATHEMATICS AND COMPUTING↗

Project Overview: LA07-LAB072-PD02

The goal of this project was to identify and characterize sources of plutonium processing signatures, and understand how fate and transport impact these signatures, with an emphasis on establishing a foundation for the use of aerosolized particle characteristics as indicators of historic and current activities within a facility. Targeted activities included: 1) Pu metal reprocessing via direct oxide reduction, 2) Breakout of α-phase and δ-phase materials, 3) CNC machining of alloyed, δ-phase Pu metal, and 4) Low speed cutting of unalloyed, α-phase metal and alloyed, δ-phase Pu metal.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Gamma-ray mirror technology for NDA of spent fuel

Direct measurements of gamma rays emitted by fissile material have been proposed as an alternative to measurements of the gamma rays from fission products. From a safeguards applications perspective, direct detection of uranium (U) and plutonium (Pu) K-shell fluorescence emission lines and specific lines from some of their isotopes could lead to improved shipper-receiver difference or input accountability at the start of Pu reprocessing. However, these measurements are difficult to implement when the spent fuel is in the line-of-sight of the detector, as the detector is exposed to high rates dominated by fission product emissions. To overcome the combination of high rates and high background, grazing incidence multilayer mirrors have been proposed as a solution to selectively reflect U and Pu hard X-ray and soft gamma rays in the 90 to 420 keV energy into a high-purity germanium (HPGe) detector shielded from the direct line-of-sight of spent fuel. Several groups demonstrated that K-shell fluorescence lines of U and Pu in spent fuel could be detected with Ge detectors. In the field of hard X-ray optics the performance of reflective multilayer coated reflective optics was demonstrated up to 645 keV at the European Synchrotron Radiation Facility. Initial measurements conducted at Oak Ridge National Laboratory with sealed sources and scoping experiments conducted at the ORNL Irradiated Fuels Examination Laboratory (IFEL) with spent nuclear fuel further demonstrated the pass-band properties of multilayer mirrors for reflecting specific emission lines into 1D and 2D HPGe detectors, respectively.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Multi-Column Kr/Xe Separation Testing at Representative Superficial Velocities with DGOSPREY Model Validation

Previous testing of AgZ-PAN and HZ-PAN for the separation and removal of xenon and krypton from air have been promising. This report details the results of multi-column testing at superficial velocities chosen to emulate probably velocities in a full-scale used nuclear fuel reprocessing facility. Additionally, results were used to validate the DG-OSPREY model under development at Georgia Institute of Technology.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Materials and Methods for Streamlined Laboratory Analysis of Environmental Samples, FY 2016 Report

The International Atomic Energy Agency (IAEA) relies upon laboratory analysis of environmental samples (typically referred to as “swipes”) collected during on-site inspections of safeguarded facilities to support the detection and deterrence of undeclared activities. Unfortunately, chemical processing and assay of the samples is slow and expensive. A rapid, effective, and simple extraction process and analysis method is needed to provide certified results with improved timeliness at reduced costs (principally in the form of reduced labor), while maintaining or improving sensitivity and efficacy. To address these safeguard needs the Pacific Northwest National Laboratory (PNNL) explored and demonstrated improved methods for environmental sample (ES) analysis. Improvements for both bulk and particle analysis were explored. To facilitate continuity and adoption, the new sampling materials and processing methods will be compatible with existing IAEA protocols for ES analysis. PNNL collaborated with Oak Ridge National Laboratory (ORNL), which performed independent validation of the new bulk analysis methods and compared performance to traditional IAEA’s Network of Analytical Laboratories (NWAL) protocol. ORNL efforts are reported separately. This report describes PNNL’s FY 2016 progress, which was focused on analytical application supporting environmental monitoring of uranium enrichment plants and nuclear fuel processing. In the future the technology could be applied to other safeguard applications and analytes related to fuel manufacturing, reprocessing, etc. PNNL’s FY 2016 efforts were broken into two tasks and a summary of progress, accomplishments and highlights are provided below. Principal progress and accomplishments on Task 1, Optimize Materials and Methods for ICP-MS Environmental Sample Analysis, are listed below. • Completed initial procedure for rapid uranium extraction from ES swipes based upon carbonate-peroxide chemistry (delivered to ORNL for evaluation). • Explored improvements to carbonate-peroxide rapid uranium extraction chemistry. • Evaluated new sampling materials and methods (in collaboration with ORNL). • Demonstrated successful ES extractions from standard and novel swipes for a wide range uranium compounds of interest including UO 2 F 2 and UO 2 (NO 3 ) 2 , U 3 O 8 and uranium ore concentrate. • Completed initial discussions with commercial suppliers of PTFE swipe materials. • Submitted one manuscript for publication. Two additional drafts are being prepared. Principal progress and accomplishments on Task 2, Optimize Materials and Methods for Direct SIMS Environmental Sample Analysis, are listed below. • Designed a SIMS swipe sample holder that retrofits into existing equipment and provides simple, effective, and rapid mounting of ES samples for direct assay while enabling automation and laboratory integration. • Identified preferred conductive sampling materials with better performance characteristics. • Ran samples on the new PNNL NWAL equivalent Cameca 1280 SIMS system. • Obtained excellent agreement between isotopic ratios for certified materials and direct SIMS assay of very low levels of LEU and HEU UO 2 F 2 particles on carbon fiber sampling material. Sample activities range from 1 to 500 CPM (uranium mass on sample is dependent upon specific isotope ratio but is frequently in the subnanogram range). • Found that the presence of the UF molecular ions, as measured by SIMS, provides chemical information about the particle that is separate from the uranium isotopics and strongly suggests that those particles originated from an UF6 enrichment activity. • Submitted one manuscript for publication. Another manuscript is in preparation.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Evaluation of Iodine Remediation Technologies in Subsurface Sediments: Interim Status Report

Isotopes of iodine were generated during plutonium production from nine production reactors at the U.S. Department of Energy Hanford Site. The long half-life 129I generated at the Hanford Site during reactor operations was 1) stored in single-shell and double-shell tanks, 2) discharged to liquid disposal sites (e.g., cribs and trenches), 3) released to the atmosphere during fuel reprocessing operations, or 4) captured by off-gas absorbent devices (silver reactors) at chemical separations plants (PUREX, B-Plant, T-Plant, and REDOX). Releases of 129I to the subsurface have resulted in several large, though dilute, plumes in the groundwater, including the plume in the 200-UP-1 operable unit. There is also 129I remaining in the vadose zone beneath disposal or leak locations. Because 129I is an uncommon contaminant, relevant remediation experience and scientific literature are limited.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Conceptual Model of Iodine Behavior in the Subsurface at the Hanford Site

Isotopes of iodine were generated during plutonium production within the nine production reactors at the U.S. Department of Energy Hanford Site. The short half-life 131I that was released from the fuel into the atmosphere during the dissolution process (when the fuel was dissolved) in the Hanford Site 200 Area is no longer present at concentrations of concern in the environment. The long half-life 129I generated at the Hanford Site during reactor operations was (1) stored in single-shell and double-shell tanks, (2) discharged to liquid disposal sites (e.g., cribs and trenches), (3) released to the atmosphere during fuel reprocessing operations, or (4) captured by off-gas absorbent devices (silver reactors) at chemical separations plants (PUREX, B-Plant, T-Plant, and REDOX). Releases of 129I to the subsurface have resulted in several large, though dilute, plumes in the groundwater. There is also 129I remaining in the vadose zone beneath disposal or leak locations. The fate and transport of 129I in the environment and potential remediation technologies are currently being studied as part of environmental remediation activities at the Hanford Site. A conceptual model describing the nature and extent of subsurface contamination, factors that control plume behavior, and factors relevant to potential remediation processes is needed to support environmental remedy decisions. Because 129I is an uncommon contaminant, relevant remediation experience and scientific literature are limited. In addition, its behavior in subsurface is different from that of other more common and important contaminants (e.g., U, Cr and Tc) in terms of sorption (adsorption and precipitation), and aqueous phase species transformation via redox reactions. Thus, the conceptual model also needs to both describe known contaminant and biogeochemical process information and identify aspects about which additional information is needed to effectively support remedy decisions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Advanced Fuel Cycle Cost Basis – 2017 Edition

This report, commissioned by the U.S. Department of Energy (DOE) Office of Nuclear Energy (NE), provides a comprehensive set of cost data supporting a cost analysis for the relative economic comparison of options for use in the DOE Nuclear Technology Research and Development (NTRD) Program (previously the Fuel Cycle Research and Development (FCRD) and the Advanced Fuel Cycle Initiative (AFCI)). The report describes the NTRD cost basis development process, reference information on NTRD cost modules, a procedure for estimating fuel cycle costs, economic evaluation guidelines, and a discussion on the integration of cost data into economic computer models. This report contains reference cost data for numerous fuel cycle cost modules (modules A-O) as well as cost modules for a number of reactor types (R modules). The fuel cycle cost modules were developed in the areas of natural uranium mining and milling, thorium mining and milling, conversion, enrichment, depleted uranium disposition, fuel fabrication, interim spent fuel storage, reprocessing, waste conditioning, spent nuclear fuel (SNF) packaging, long-term monitored retrievable storage, managed decay storage, recycled product storage, near surface disposal of low-level waste (LLW), geologic repository and other disposal concepts, and transportation processes for nuclear fuel, LLW, SNF, transuranic, and high-level waste. Since its inception, this report has been periodically updated. The last such internal document was published in August 2015 while the last external edition was published in December of 2009 as INL/EXT-07-12107 and is available on the Web at URL: www.inl.gov/technicalpublications/Documents/4536700.pdf. This current report (Sept 2017) is planned to be reviewed for external release, at which time it will replace the 2009 report as an external publication. This information is used in the ongoing evaluation of nuclear fuel cycles by the NE NTRD program.

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Milestone Report - Data Requirements and Test System Needs for Development of an Integrated Off-Gas Treatment System

In fiscal year 2016 an Engineering Evaluation of an integrated off-gas system was conducted. This study resulted in a report entitled Engineering Evaluation of an Integrated Off-Gas Treatment System for Used Nuclear Fuel Reprocessing Facilities (Jubin et al. 2016a), from here referred to as the “Engineering Evaluation.” This study focused on the capture and retention of the volatile radionuclides ( 3 H, 14 C, 85 Kr, and 129 I), selected semi-volatile radionuclides, specifically 106 Ru, and chemical species like NO and NO 2 generated during the dissolution of the used nuclear fuel. The study examined the design of the combined head-end off-gas streams and the vessel off-gas stream. The study drew upon the available literature to conduct the equipment sizing and sorbent usage. A number of assumptions were required to complete this analysis and major gaps in the available data were identified that, if resolved, could increase the fidelity of the engineering design.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Cross-Calibration of the GPS Constellation CXD Proton Data with GOES EPS [Slides]

The CXD provides good quality proton flux measurements across a range of proton energies. The data within the 1 st and 3 rd quartile range of the ratio of integral flux values is within 20 – 40%. While proton response of the CXD extends down to 6 MeV due to collimator holes in instrument filters, the > 10 MeV integral proton flux is not well captured as shown by the comparisons with EPS. We recommend that users of the data restrict their analysis to proton energies > 20 MeV. Although the full dataset is available now [https://www.ngdc.noaa.gov/stp/spaceweather/satellite-data/satellite-systems/gps/] this updated flux calculation is not present and so a reprocessing will commence soon and the dataset updated. These calibrated datasets will allow a number of exciting multipoint analyses such as more accurate probing of geomagnetic cutoffs as well as providing additional input to radiation belt climatology models such as AE9/AP9/SPM [Ginet et al., 2013].

58 GEOSCIENCES↗

Literature Review: Crud Formation at the Liquid/Liquid Interface of TBP-Based Solvent-Extraction Processes

This report summarizes the literature reviewed on crud formation at the liquid:liquid interface of solvent extraction processes. The review is focused both on classic PUREX extraction for industrial reprocessing, especially as practiced at the Hanford Site, and for those steps specific to plutonium purification that were used at the Plutonium Reclamation Facility (PRF) within the Plutonium Finishing Plant (PFP) at the Hanford Site.

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Final Technical Report: Imaging a Dry Storage Cask with Cosmic Ray Muons

The goal of this project is to build a scaled prototype system for monitoring used nuclear fuel (UNF) dry storage casks (DSCs) through cosmic ray muon imaging. Such a system will have the capability of verifying the content inside a DSC without opening it. Because of the growth of the nuclear power industry in the U.S. and the policy decision to ban reprocessing of commercial UNF, the used fuel inventory at commercial reactor sites has been increasing. Currently, UNF needs to be moved to independent spent fuel storage installations (ISFSIs), as its inventory approaches the limit on capacity of on-site wet storage. Thereafter, the fuel will be placed in shipping containers to be transferred to a final disposal site. The ISFSIs were initially licensed as temporary facilities for ~20-yr periods. Given the cancellation of the Yucca mountain project and no clear path forward, extended dry-cask storage (~100 yr.) at ISFSIs is very likely. From the point of view of nuclear material protection, accountability and control technologies (MPACT) campaign, it is important to ensure that special nuclear material (SNM) in UNF is not stolen or diverted from civilian facilities for other use during the extended storage.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development and Optimization of Voltammetric Methods for Real Time Analysis of Electrorefiner Salt with High Concentrations of Actinides and Fission Products

This project addresses the problem of achieving accurate material control and accountability (MC&A) around pyroprocessing electrorefiner systems. Spent nuclear fuel pyroprocessing poses a unique challenge with respect to reprocessing technology in that the fuel is never fully dissolved in the process fluid. In this case, the process fluid is molten, anhydrous LiCl-KCl salt. Therefore, there is no traditional input accountability tank. However, electrorefiners (ER) accumulate very large quantities of fissile nuclear material (including plutonium) and should be well safeguarded in a commercial facility. Idaho National Laboratory (INL) currently operates a pyroprocessing facility for treatment of spent fuel from Experimental Breeder Reactor-II with two such ER systems. INL implements MC&A via a mass tracking model in combination with periodic sampling of the salt and other materials followed by destructive analysis. This approach is projected to be insufficient to meet international safeguards timeliness requirements. A real time or near real time monitoring method is, thus, direly needed to support commercialization of pyroprocessing. A variety of approaches to achieving real time monitoring for ER salt have been proposed and studied to date—including a potentiometric actinide sensor for concentration measurements, a double bubbler for salt depth and density measurements, and laser induced breakdown spectroscopy (LIBS) for concentration measurements. While each of these methods shows some promise, each also involves substantial technical complexity that may ultimately limit their implementation. Yet another alternative is voltammetry —a very simple method in theory that has previously been tested for this application to a limited extent. The equipment for a voltammetry system consists of off-the-shelf components (three electrodes and a potentiostat), which results in substantial benefits relative to cost and robustness. Based on prior knowledge of electrochemical reduction potentials for each of the species of interest, voltammetry can be used to quantify concentrations of a variety of elemental species—including uranium, plutonium, minor actinides, and rare earths. Various methods have been tested by other researchers to date—including cyclic voltammetry, square wave voltammetry, normal pulse voltammetry, etc. In most cases, it has been observed that there is a very limited concentration range for which the output can be readily correlated with concentration in the salt. Furthermore, testing to date has been limited to simple ternary salts with only a single element being quantified. While incomplete for application to MC&A for pyroprocessing, these results lead us to believe that voltammetry can be optimized based on salt properties and fundamental electrochemical rate processes to yield a highly accurate and robust method. This project is divided into four tasks jointly executed by three university research groups. This includes experimental measurement of key physical data on the systems of interest, development of a predictive voltammetry model, experimental validation of the voltammetry model, and design/verification of an optimized measurement method. This project supports the goals of the US-ROK Joint Fuel Cycle Study in addition to the NA-24 Office of the National Nuclear Security Agency and the International Atomic Energy Agency (IAEA).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Thermally and chemically responsive nanoporous materials for efficient capture of fission product gases.

The objective of this project was to develop robust, high-efficiency materials for capture of fission product gases such as He, Xe and Kr in scenarios relevant for both reactor fuels and reprocessing operations. The relevant environments are extremely harsh, encompassing temperatures up to 1500 °C, high levels of radiation, as well as potential exposures to highly-reactive chemicals such as nitric acid and organic solvents such as kerosene. The requirement for nanostructured capture materials is driven in part by the very short (few micron) diffusion distances for product gases in nuclear fuel. We achieved synthesis, characterization and detailed modeling of the materials. Although not all materials reviewed in this report will be feasible for the ultimate goal of integration in nuclear fuel, nevertheless each material studied has particular properties which will enable an optimized material to be efficiently developed and characterized.

36 MATERIALS SCIENCE↗

First ARM Aerosol Chemical Speciation Monitor Users’ Meeting Report

The first U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) user facility aerosol chemical speciation monitor (ACSM) users’ meeting was held on April 11-13, 2017, at Aerodyne Research, Inc. in Billerica, Massachusetts, to discuss the Southern Great Plains (SGP) atmospheric observatory ACSM data quality and establish best practices for data collection and processing. The participants examined six years of calibration and processed data. Specific issues raised by data users were addressed and case studies from two field experiments were examined. The most recent data from the ACSM installed in the newly commissioned SGP ARM Mobile Facility 7 (AMF7) were also evaluated. The participants recommended that the SGP ACSM data be reprocessed using calibration values averaged over the history of SGP ACSM calibrations. They also recommended that the data quality be evaluated by comparing (1) observed versus predicted particulate ammonium (NH4+) mass loadings, and (2) ACSM mass loadings versus mass loadings calculated from particle size and light scattering data. The contents of the datastreams from the ACSM were defined based on ARM requirements and the necessary tasks to implement these recommendations were assigned to the mentor and the instrument manufacturer. Some of the recommendations were implemented for the SGP data and are presented in this report. Data from two ARM sites located in marine environments were also analyzed. These analyses as well as instrument intercomparisons have led to further questions about data treatment. These will be addresses in the second users’ meeting scheduled for the summer of 2018.

54 ENVIRONMENTAL SCIENCES↗

First ARM Aerosol Chemical Speciation Monitor Users’ Meeting Report

The first U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) user facility aerosol chemical speciation monitor (ACSM) users’ meeting was held on April 11-13, 2017, at Aerodyne Research, Inc. in Billerica, Massachusetts, to discuss the Southern Great Plains (SGP) atmospheric observatory ACSM data quality and establish best practices for data collection and processing. The participants examined six years of calibration and processed data. Specific issues raised by data users were addressed and case studies from two field experiments were examined. The most recent data from the ACSM installed in the newly commissioned SGP ARM Mobile Facility 7 (AMF7) were also evaluated. The participants recommended that the SGP ACSM data be reprocessed using calibration values averaged over the history of SGP ACSM calibrations. They also recommended that the data quality be evaluated by comparing (1) observed versus predicted particulate ammonium (NH 4 + ) mass loadings, and (2) ACSM mass loadings versus mass loadings calculated from particle size and light scattering data. The contents of the datastreams from the ACSM were defined based on ARM requirements and the necessary tasks to implement these recommendations were assigned to the mentor and the instrument manufacturer. Some of the recommendations were implemented for the SGP data and are presented in this report. Data from two ARM sites located in marine environments were also analyzed. These analyses as well as instrument intercomparisons have led to further questions about data treatment. These will be addresses in the second users’ meeting scheduled for the summer of 2018.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Initial Evaluation of CaSDB MOF Xe and Kr Capacities

Idaho National Laboratory (INL) and Pacific Northwest National Laboratory (PNNL) have been conducting parallel research, as part of the off-Gas Sigma Team, producing and testing sorbents for the selective capture of xenon and krypton from surrogate nuclear fuel reprocessing off-gas streams. Sorbents promising on a laboratory scale are tested further at INL in a system designed to emulate anticipated plant process conditions. This report summarizes INL’s initial testing of CaSDB MOF developed and produced at PNNL. Previous testing of the same base CaSDB MOF material, conducted at INL in 2016, indicated good saturation capacity for xenon, but a low xenon capacity at initial breakthrough. Additionally, the material displayed a propensity to break down into fine powder during use and handling. The current test series looks at the same base material, but with refinements to production and activation techniques. A series of ambient temperature tests were conducted to determine capacities of CaSDB MOF for krypton and xenon at initial breakthrough as well as at saturation. Adsorption tests were run in triplicate at superficial velocities of 21 and 53 cm/min, along with a single test at 373 cm/min. Saturation capacity across all tests was 30 mmol/kg +/- 2, with capacity at initial breakthrough of 8 mmol/kg +/- 1. It should be noted that while the usable portion of the material has a much tighter size distribution than that previously tested, propensity to physically break down into very fine powder with use and handling continues to be problematic. An improved engineered form is recommended prior to further testing

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