ABSTRACT
Selenium 79 is a beta emitter produced from (235)U fission and is one of the long half-life radionuclides of interest in nuclear waste disposal problematic because of its potential migration capacity to the surface environment. Measurement of (79)Se is particularly difficult due to its low activity in waste matrices (about 10(-3)Bqg(-1)). A radiochemical procedure based on ion exchange separations was already described in a previous paper. This work presents different applications of the radiochemical separation to waste samples and an improvement of this procedure, including a selective extraction of selenium as diethylselenium in an organic solvent followed by a re-extraction in aqueous medium. This additional step allows the decontamination factor to be increased with the aim of counting (79)Se by liquid scintillation counting.
ABSTRACT
Selenium (Se) 79 is a beta emitter produced from (235)U fission thus occurring as one of the fission products found in nuclear reactors. Due to its long half life (about 10(5) years), (79)Se is one of the radionuclides of interest for the performance of assessment studies of waste storage or disposal. Thus, the National Radioactive Waste Management Agency (Andra, France) requests its monitoring in wastes packages before their disposal in specific sites. Measurement of (79)Se is difficult owing to its trace level concentration and its low activity in nuclear wastes. A radiochemical procedure has to be carried out in order to separate selenium from the matrix and to concentrate it before the measurement with a mass spectrometric or a nuclear technique. The beginning of the development is presented in this paper. The optimised protocol firstly developed in view of an ICP-MS measurement, includes five steps based on microwave digestion, evaporation and separations on ion exchange resins. It was tested first on synthetic solutions and was optimised in order to be applicable to a large number of sample types. The recoveries of the whole procedure were evaluated using natural (82)Se or the gamma emitter (75)Se as a radioactive spiker. Then, the protocol was applied to two solid samples spiked with natural selenium, a glass microfiber filter and an ion exchange resin, and two liquid samples spiked with (75)Se, a synthetic solution and an effluent. The yields obtained for both samples ranged from 70 up to 80%.
ABSTRACT
Solid-phase microextraction (SPME) has become a real alternative to liquid-liquid extraction in the field of speciation of organometallic compounds. Despite the high performance of this preconcentration technique, matrix effects in natural samples can affect the analytical precision. In order to understand the origin of these disturbances and control the extraction step as best as possible, the sorption-desorption behaviour of organotins was studied. In the first part, this paper discusses the analytical problems encountered in the daily use of SPME due to the particular problems observed for phenyltins. The sorption profile of these compounds was modelled using experimental design methodology to confirm the first-order kinetics. Desorption of the compounds was also observed after a given time and could not be attributed to competition between organotin compounds. In the same way, butyl- and phenyltins were studied in the presence of humic substances, which acted as representatives of organic matter found in natural samples. These substances drastically decrease the extraction yields, but do not affect the sorption profile of butyl- and phenyltins.
Subject(s)
Organotin Compounds/chemistry , Humic Substances/analysisABSTRACT
The coupling between gas chromatography (GC) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) has been optimised using experimental designs. Four factors were considered in order to assist the crucial part of the coupling which is the analytes passing through the transfer line. The methodological approach based on the planning of fractional designs is described and justified according to an optimal experimentation. Then, the GC-ICP-AES-based method has been validated by means of statistical tests performed on calibration curves and evaluation of accuracy, precision and limits of detection (LOD), according to ISO standards and IUPAC recommendations. The absolute LOD are found to be quite similar to those obtained using flame photometer. Relative LOD ranged between 20 and 80 ng (Sn) L(-1) after liquid-liquid extraction of the analytes. When solid phase micro-extraction (SPME) is used, LOD are sub 10 ng (Sn) L(-1). The repeatability is 3-10%, according to the extraction used. Analyses of reference sediment, fresh and waste waters confirm the suitability and capabilities of GC-ICP-AES for organotin determination in the environment. The statistical approach has been demonstrated to be a powerful methodological tool, enhancing the experimental part by providing reliable analytical results.
