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Lee, Denise L.

Publications and source records attributed to Lee, Denise L..

Analysis of Environmental Swipes Using Fluorescence Microscopy - Summary Report

This report summarizes efforts as part of a collaboration between Oak Ridge National Laboratory (ORNL) and the University of Kansas (KU) during fiscal year 2016 for the purpose of screening environmental swipes (ESs) using fluorescence microscopy. The overall goal of this work is to image actinide-bearing species by exploiting the fluorescence properties of the uranyl moiety. If successfully developed, this capability would permit automated screening of actinide species in environmental swipes to prioritize samples for destructive analysis. The evaluation of efforts to date has shown that uranyl fluoride can be imaged using fluorescence microscopy and the vibronic structure can be resolved; however, difficulties arise when attempting to image these materials on ESs because of spectral interference. Due to the fluorescence decay differences between cellulosic fibers and uranyl-containing materials, time-gating approaches were investigated to minimize this interference. This approach shows promise; however, the technique requires additional developmental work before it can be transitioned to a robust method for laboratory use.

54 ENVIRONMENTAL SCIENCES↗

Validation of gamma-ray detection techniques for safeguards monitoring at natural uranium conversion facilities

Recent IAEA circulars and policy papers have sought to implement safeguards when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under the revised policy, IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed to develop and validate concepts of nondestructive assay monitoring systems in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO 2 (NO 3 ) 2 ) solution exiting solvent extraction was identified as a key measurement point (KMP), where gamma-ray spectroscopy was selected as the process monitoring tool. The Uranyl Nitrate Calibration Loop Equipment (UNCLE) facility at Oak Ridge National Laboratory was employed to simulate the full-scale operating conditions of a purified uranium-bearing aqueous stream exiting the solvent extraction process in an NUCP. Nondestructive assay techniques using gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely way. This work investigated gamma-ray signatures of uranyl nitrate circulating in the UNCLE facility and evaluated various gamma-ray detector sensitivities to uranyl nitrate. These detector validation activities include assessing detector responses to the uranyl nitrate gamma-ray signatures for spectrometers based on sodium iodide, lanthanum bromide, and high-purity germanium detectors. The results of measurements under static and dynamic operating conditions at concentrations ranging from 10–90 g U/L of natural uranyl nitrate are presented. A range of gamma-ray lines is examined, including attenuation for transmission measurement of density and concentration. It was determined that transmission-corrected gamma-ray spectra provide a reliable way to monitor the 235 U concentration of uranyl nitrate solution in transfer pipes in NUCPs. Furthermore, existing predictive and analysis methods are adequate to design and realize practical designs. The 137 Cs transmission source employed in this work is viable but not optimal for 235 U densitometry determination. Validated simulations assessed the viability of 133 Ba and 57Co as alternative densitometry sources. All three gamma-ray detectors are viable for monitoring natural uranium feed; although high-purity germanium is easiest to interpret, it is, however, the least attractive as an installation instrument. Overall, for monitoring throughput in a facility such as UNCLE, emulating the uranium concentration and pump speeds of the Springfields conversion facility in the United Kingdom, an uncertainty of less than 0.17% is required in order to detect the diversion of 1 SQ of uranyl nitrate through changes in uranium concentration over an accountancy period of one year with a detection probability of 50%. As a result, calibrated gamma-ray detection systems are capable of determining the concentration of uranium content in NUCPs, it is only in combination with verifiable operator declarations and supporting data, such as flow rate and enrichment, that safeguards conclusions can be drawn.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Technologies for pre-screening IAEA swipe samples

During the course of International Atomic Energy Agency (IAEA) inspections, many samples are taken for the purpose of verifying the declared facility activities and identifying any possible undeclared activities. One of these sampling techniques is the environmental swipe sample. Due to the large number of samples collected, and the amount of time that is required to analyze them, prioritizing these swipes in the field or upon receipt at the Network of Analytical Laboratories (NWAL) will allow sensitive or mission-critical analyses to be performed sooner. As a result of this study, technologies were placed into one of three categories: recommended, promising, or not recommended. Both neutron activation analysis (NAA) and X-ray fluorescence (XRF) are recommended for further study and possible field deployment. These techniques performed the best in initial trials for pre-screening and prioritizing IAEA swipes. We learned that for NAA more characterization of cold elements (such as calcium and magnesium) would need to be emphasized, and for XRF it may be appropriate to move towards a benchtop XRF versus a handheld XRF due to the increased range of elements available on benchtop equipment. Promising techniques that will require additional research and development include confocal Raman microscopy, fluorescence microscopy, and infrared (IR) microscopy. These techniques showed substantive responses to uranium compounds, but expensive instrumentation upgrades (confocal Raman) or university engagement (fluorescence microscopy) may be necessary to investigate the utility of the techniques completely. Point-and-shoot (handheld) Raman and attenuated total reflectance–infrared (ATR-IR) measurements are not recommended, as they have not shown enough promise to continue investigations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Technology recommendations for pre-screening of IAEA swipe samples

Argonne and Oak Ridge National Laboratories have prepared an analysis of recommended, possible, and not recommended technologies for pre-screening and prioritizing IAEA swipes. The analytical techniques listed under the recommended technology list are the most promising techniques available to date. The recommended list is divided into two sections: Argonne’s recommended techniques and Oak Ridge’s recommended techniques. This list was divided based upon the expertise of staff in each subject area and/or the instrumentation available at each laboratory. The following section, titled Possible Techniques, is a list of analytical techniques that could be used for pre-screening and prioritizing swipes if additional instrumentation and effort were provided. These techniques are not necessarily top priority, but should not be discounted for future or expanded efforts. Lastly, a list of not recommended techniques is provided to outline the analytical methods and instrumentation that were investigated by each lab but deemed not suitable for this task. In addition to the recommendation list, a short procedure is provided outlining the steps followed for destructive analysis by the Network of Analytical Laboratories (NWAL) for determination of uranium concentrations, isotopic content of sample and swipe. Swipes generated for this project will be given to ORNL’s NWAL laboratory for analysis after analysis by other techniques at both laboratories.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Radiolytic Treatment of the Next-Generation Caustic-Side Solvent Extraction (NGS) Solvent and its Effect on the NGS Process

We show in this work that the solvent used in the Next Generation Caustic-Side Solvent Extraction (NGS) process can withstand a radiation dose well in excess of the dose it would receive in multiple years of treating legacy salt waste at the US Department of Energy Savannah River Site. The solvent was subjected to a maximum of 50 kGy of gamma radiation while in dynamic contact with each of the aqueous phases of the current NGS process, namely SRS-15 (a highly caustic waste simulant), sodium hydroxide scrub solution (0.025 M), and boric acid strip solution (0.01 M). Bench-top testing of irradiated solvent confirmed that irradiation has inconsequential impact on the extraction, scrubbing, and stripping performance of the solvent up to 13 times the estimated 0.73 kGy/y annual absorbed dose. Lastly, stripping performance is the most sensitive step to radiation, deteriorating more due to buildup of p-sec-butylphenol (SBP) and possibly other proton-ionizable products than to degradation of the guanidine suppressor, as shown by chemical analyses.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Next Generation Solvent (NGS): Development for Caustic-Side Solvent Extraction of Cesium

This report summarizes the FY 2010 and 2011 accomplishments at Oak Ridge National Laboratory (ORNL) in developing the Next Generation Caustic-Side Solvent Extraction (NG-CSSX) process, referred to commonly as the Next Generation Solvent (NGS), under funding from the U.S. Department of Energy, Office of Environmental Management (DOE-EM), Office of Technology Innovation and Development. The primary product of this effort is a process solvent and preliminary flowsheet capable of meeting a target decontamination factor (DF) of 40,000 for worst-case Savannah River Site (SRS) waste with a concentration factor of 15 or higher in the 18-stage equipment configuration of the SRS Modular Caustic-Side Solvent Extraction Unit (MCU). In addition, the NG-CSSX process may be readily adapted for use in the SRS Salt Waste Processing Facility (SWPF) or in supplemental tank-waste treatment at Hanford upon appropriate solvent or flowsheet modifications. Efforts in FY 2010 focused on developing a solvent composition and process flowsheet for MCU implementation. In FY 2011 accomplishments at ORNL involved a wide array of chemical-development activities and testing up through single-stage hydraulic and mass-transfer tests in 5-cm centrifugal contactors. Under subcontract from ORNL, Argonne National Laboratory (ANL) designed a preliminary flowsheet using ORNL cesium distribution data, and Tennessee Technological University confirmed a chemical model for cesium distribution ratios (DCs) as a function of feed composition. Interlaboratory efforts were coordinated with complementary engineering tests carried out (and reported separately) by personnel at Savannah River National Laboratory (SRNL) and Savannah River Remediation (SRR) with helpful advice by Parsons Engineering and General Atomics on aspects of possible SWPF implementation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗