PNNL

Abstract

Advanced techniques enabling enhanced safeguarding of the spent fuel reprocessing plants are urgently needed. Our approach is based on prerequisite that real time monitoring of the solvent extraction flowsheets provides unique capability to quickly detect unwanted manipulations with fissile isotopes present in the radiochemical streams during reprocessing activities. The methods used to monitor these processes must be robust and must be able to withstand harsh radiation and chemical environments. A new on-line monitoring system satisfying these requirements and featuring Raman spectroscopy combined with a Coriolis and conductivity probes, has been recently developed by our research team. It provides immediate chemical data and flow parameters of high-level radioactive waste streams with high brine content generated during retrieval activities from Hanford nuclear waste storage tanks. The nature of the radiochemical streams at the spent fuel reprocessing plant calls for additional spectroscopic information, which can be gained by the utilization of UV-vis-NIR capabilities. Raman and UV-vis-NIR spectroscopies are analytical techniques that have extensively been extensively applied for measuring the various organic and inorganic compounds including actinides. The corresponding spectrometers used under the laboratory conditions are easily convertible to the process-friendly configurations allowing remote measurements under the flow conditions. A fiber optic Raman probe allows monitoring of the high concentration species encountered in both aqueous and organic phases within the UREX suite of flowsheets, including metal oxide ions, such as uranyl, components of the organic solvent, inorganic oxo-anions, and water. The actinides and lanthanides are monitored remotely by UV-vis-NIR spectroscopy in aqueous and organic phases. In this report, we will present our recent results on spectroscopic measurements of simulant flowsheet solutions and commercial fuels available at PNNL. Measurements are performed at wide range of conditions adjusted to mimic UREX/PUREX processes and to demonstrate the applicability of Raman and vis-NIR spectroscopic analysis for actual dissolver feed solutions.