Evaluation of kinetic phosphorescence analysis for the determination of uranium

Abstract

In the past, New Brunswick Laboratory (NBL) has used a fluorometric method for the determination of sub-microgram quantities of uranium. In its continuing effort to upgrade and improve measurement technology, NBL has evaluated the commercially-available KPA-11 kinetic phosphorescence analyzer (Chemchek, Richland, WA). The Chemchek KPA-11 is a bench-top instrument which performs single-measurement, quench-corrected analyses for trace uranium. It incorporates patented kinetic phosphorimetry techniques to measure and analyze sample phosphorescence as a function of time. With laser excitation and time-corrected photon counting, the KPA-11 has a lower detection limit than conventional fluorometric methods. Operated with a personal computer, the state-of-the-art KPA-11 offers extensive time resolution and phosphorescence lifetime capabilities for additional specificity. Interferences are thereby avoided while obtaining precise measurements. Routine analyses can be easily and effectively accomplished, with the accuracy and precision equivalent to the pulsed-laser fluorometric method presently performed at NBL, without the need for internal standards. Applications of kinetic phosphorimetry at NBL include the measurement of trace level uranium in retention tank, waste samples, and low-level samples. It has also been used to support other experimental activities at NBL by the measuring of nanogram amounts of uranium contamination (in blanks) in isotopic sample preparations, and the determining of elution curves of different ion exchange resins used for uranium purification. In many cases, no pretreatment of samples was necessary except to fume them with nitric acid, and then to redissolve and dilute them to an appropriate concentration with 1 M HNO{sub 3} before measurement. Concentrations were determined on a mass basis ({micro}g U/g of solution), but no density corrections were needed since all the samples (including the samples used for calibration) were in the same density matrix (1 M HNO{sub 3}). A statistical evaluation of the determination of uranium using kinetic phosphorimetry is described in this report, along with a discussion of the method, and an evaluation of the use of plastic versus quartz cuvettes. Measurement with a precision of {+-} 3--4% relative standard deviation (RSD) and an accuracy of better than {+-} 2% relative difference (RD) are obtained in the 0.0006 to 5 {micro}g U/g-solution range. The instrument detection limit is 0.04 ppb (4 x 10{sup {minus}5} {micro}g U/g solution) using quartz cells, and 0.11 ppb (11 x 10{sup {minus}5} {micro}g U/g solution) using disposable methacrylate cuvettes.