PNNL

Abstract

Abstract – Significant effort has been focused on the back end of the nuclear fuel cycle including treatment and reuse of irradiated fuel. Solvent extraction reprocessing methods that have been developed often contain various steps, with each one tailored to the separation of specific radionuclides, which are highly dependent upon solution properties. The instrumentation used to monitor these processes must be robust, require little or no maintenance, and be able to withstand harsh environments such as high radiation fields and aggressive chemical matrices. Our group has been investigating the use of optical spectroscopy for the on-line monitoring of actinides, lanthanides, and acid strength within fuel reprocessing streams. This paper describes the application of the electronic and vibrational spectroscopic techniques for radiochemical process monitoring. In this context, our team experimentally assessed the potential of Raman and UV-vis spectroscopic techniques for online real-time monitoring of the U(VI)/nitrate ion/nitric acid and Pu(VI/IV)/Np(VI/V/IV)/Nd(III) in solutions relevant to used nuclear fuel reprocessing. These techniques demonstrated robust performance in the repetitive batch measurements of each analyte in a wide concentration range using simulant and commercial dissolved used fuel solutions. Currently this has been demonstrated on the macroscopic scale, using sample probes requiring large solution volumes. In an effort to minimize waste and reduce dose to personnel, we have modified this technique to allow measurement at the microfluidic scale using a Raman microprobe. Under the current sampling environment, Raman samples typically require upwards of 10 mL and larger. Using the new sampling system, we can sample volumes at 10 µL or less, which is a scale reduction of over 1,000 fold in sample size. This will significantly reduce the requirements for handling hazardous materials, and greatly reduce the costs associated with worker protection from exposure to radioactive and hazardous materials, and costs due to waste disposal.