High resolution inductively coupled plasma mass spectrometry for the trace determination of plutonium isotopes and isotope ratios in environmental samples

A high resolution inductively coupled plasma mass spectrometric (HR-ICP-MS) method for the determination of plutonium isotopes and the Pu-240/Pu-239 isotope ratio utilising ultrasonic nebulisation was developed. Total plutonium concentrations (Pu239+240) measured in environmental samples by this HR-ICP-MS method were in good agreement with data obtained from alpha-spectrometry. Quantification was performed by both external calibration and isotope dilution and the best agreement was found by applying isotope dilution. Detection limits of 5, 1 and 1 fg ml(-1) were found for Pu-239, Pu-240 and Pu-242, respectively. These represent total amounts of 50, 10 and 10 fg or 0.1, 0.08 and 0.002 mBq of the three isotopes in a 10 mi sample volume. The precision (RSD) on the measurement of the Pu-240/Pu-239 ratio in environmental samples was approximately 2%, which is close to the theoretical precision (Poisson statistics). The influence of dwell time, number of sweeps and sample uptake rate on the measurement precision of the Pu-240/Pu-239 isotope ratio was investigated and the parameters were optimised using a 23 experimental design (a central composite design followed by a ridge;analysis). The accuracy of the isotope ratio measurement was evaluated by comparing results from this HR-ICP-MS method with results from high resolution a-spectrometry and spectral deconvolution. Good agreement was found between the two techniques.