Hahn, P. A. | Engineering Papers

DOE OSTI2015

Transition of Iodine Analysis to Accelerator Mass Spectrometry

The goal of the project, New Paradigms for Isotope Ratio Mass Spectrometry: Raising the Scientific Profile and Improved Performance for Accelerator Mass Spectrometry (AMS) and Thermal Ionization Mass Spectrometry (TIMS), is to ensure that the ongoing isotope ratio determination capability within the U.S. Department of Energy complex is the world’s best for application to nonproliferation. This report spells out the progress of Task 4, Transition of TIMS to AMS for Iodine Analysis, of the larger project. The subtasks under Task 4 and the accomplishments throughout the three year project life cycle are presented in this report. Progress was made in optimization of chemical extraction, determination of a detection limit for 127Iodine, production of standard materials for AMS analysis quality assurance, facilitation of knowledge exchange with respect to analyzing iodine on an AMS, cross comparison with a world-leading AMS laboratory, supercritical fluid extraction of iodine for AMS analysis and electrodeposition of seawater as a direct method of preparation for iodine analysis by AMS--all with the goal of minimizing the time required to stand up an AMS capability for iodine analysis of exposed air filters at INL. An effective extraction method has been developed and demonstrated for iodine analysis of exposed air filters. Innovative techniques to accomplish the cathode preparation for AMS analysis were developed and demonstrated and published. The known gap of a lack of available materials for reference standards in the analysis of iodine by AMS was filled by the preparation of homogenous materials that were calibrated against NIST materials. A minimum limit on the amount of abundant isotope in a sample was determined for AMS analysis. The knowledge exchange occurred with fantastic success. Scientists engaged the international AMS community at conferences, as well as in their laboratories for collaborative work. The supercritical fluid extraction work has positive data, but is not a replacement for leaching yet. The added seawater work has led to a good method and a possible publication. The focus of this project was to minimize the time to stand up the AMS capability, by having all the preparation and supporting functions worked out ahead of the instrument arrival. Due to all the preparatory work and its success, the instrument was delivered and turned over to the INL in February 2015. Since then, INL scientists have been successfully vetting the capabilities and accomplishing their own measurements that agree well with the leading laboratories of the world for iodine analysis by AMS. Initially, all AMS data was gathered on other laboratories instruments, but during the last six months data for this project has come from INL’s AMS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Microfluidic-Based sample chips for radioactive solutions

Historical nuclear fuel cycle process sampling techniques required sample volumes ranging in the tens of milliliters. The radiation levels experienced by analytical personnel and equipment, in addition to the waste volumes generated from analysis of these samples, have been significant. These sample volumes also impacted accountability inventories of required analytes during process operations. To mitigate radiation dose and other issues associated with the historically larger sample volumes, a microcapillary sample chip was chosen for further investigation. The ability to obtain microliter volume samples coupled with a remote automated means of sample loading, tracking, and transporting to the analytical instrument would greatly improve analytical efficiency while reducing both personnel exposure and radioactive waste volumes. Sample chip testing was completed to determine the accuracy, repeatability, and issues associated with the use of microfluidic sample chips used to supply µL sample volumes of lanthanide analytes dissolved in nitric acid for introduction to an analytical instrument for elemental analysis.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2014

Microfluidic-Based Sample Chips for Radioactive Solutions

Historical nuclear fuel cycle process sampling techniques required sample volumes ranging in the tens of milliliters. The radiation levels experienced by analytical personnel and equipment, in addition to the waste volumes generated from analysis of these samples, have been significant. These sample volumes also impacted accountability inventories of required analytes during process operations. To mitigate radiation dose and other issues associated with the historically larger sample volumes, a microcapillary sample chip was chosen for further investigation. The ability to obtain microliter volume samples coupled with a remote automated means of sample loading, tracking, and transporting to the analytical instrument would greatly improve analytical efficiency while reducing both personnel exposure and radioactive waste volumes. Sample chip testing was completed to determine the accuracy, repeatability, and issues associated with the use of microfluidic sample chips used to supply µL sample volumes of lanthanide analytes dissolved in nitric acid for introduction to an analytical instrument for elemental analysis.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2013

Characterization of Irradiated Metal Waste from the Pyrometallurgical Treatment of Used EBR-II Fuel

As part of the pyrometallurgical treatment of used Experimental Breeder Reactor-II fuel, a metal waste stream is generated consisting primarily of cladding hulls laden with fission products noble to the electrorefining process. Consolidation by melting at high temperature [1873 K (1600 degrees C)] has been developed to sequester the noble metal fission products (Zr, Mo, Tc, Ru, Rh, Te, and Pd) which remain in the iron-based cladding hulls. Zirconium from the uranium fuel alloy (U-10Zr) is also deposited on the hulls and forms Fe-Zr intermetallics which incorporate the noble metals as well as residual actinides during processing. Hence, Zr has been chosen as the primary indicator for consistency of the metal waste. Recently, the first production-scale metal waste ingot was generated and sampled to monitor Zr content for Fe-Zr intermetallic phase formation and validation of processing conditions. Chemical assay of the metal waste ingot revealed a homogeneous distribution of the noble metal fission products as well as the primary fuel constituents U and Zr. Microstructural characterization of the ingot confirmed the immobilization of the noble metals in the Fe-Zr intermetallic phase.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2011

Reference Alloy Waste Form Fabrication and Initiation of Reducing Atmosphere and Reductive Additives Study on Alloy Waste Form Fabrication

This report describes the fabrication of two reference alloy waste forms, RAW-1(Re) and RAW-(Tc) using an optimized loading and heating method. The composition of the alloy materials was based on a generalized formulation to process various proposed feed streams resulting from the processing of used fuel. Waste elements are introduced into molten steel during alloy fabrication and, upon solidification, become incorporated into durable iron-based intermetallic phases of the alloy waste form. The first alloy ingot contained surrogate (non-radioactive), transition-metal fission products with rhenium acting as a surrogate for technetium. The second alloy ingot contained the same components as the first ingot, but included radioactive Tc-99 instead of rhenium. Understanding technetium behavior in the waste form is of particular importance due the longevity of Tc-99 and its mobility in the biosphere in the oxide form. RAW-1(Re) and RAW-1(Tc) are currently being used as test specimens in the comprehensive testing program investigating the corrosion and radionuclide release mechanisms of the representative alloy waste form. Also described in this report is the experimental plan to study the effects of reducing atmospheres and reducing additives to the alloy material during fabrication in an attempt to maximize the oxide content of waste streams that can be accommodated in the alloy waste form. Activities described in the experimental plan will be performed in FY12. The first aspect of the experimental plan is to study oxide formation on the alloy by introducing O 2 impurities in the melt cover gas or from added oxide impurities in the feed materials. Reducing atmospheres will then be introduced to the melt cover gas in an attempt to minimize oxide formation during alloy fabrication. The second phase of the experimental plan is to investigate melting parameters associated with alloy fabrication to allow the separation of slag and alloy components of the melt.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗