Combined use of medium mass resolution and desolvation introduction system for accurate plutonium determination in the femtogram range by inductively coupled plasma-sector-field mass spectrometry

Abstract

Formation of a polyatomic species made of an atom of a heavy element like lead, mercury or iridium, and atoms abundant in plasma (argon, nitrogen, oxygen, and hydrogen) when using an inductively coupled plasma-sector-field mass spectrometer (ICP-SFMS) may lead to false detection of femtograms (fg) of plutonium or bias in the measured concentrations. Mathematical corrections, based on the measurement of heavy element concentrations in the sample solutions and determination of the extents of formation of the polyatomic interferences, are efficient but time-consuming and degrade detection limits. We describe and discuss a new method based on the combination of, on the one hand, medium mass resolution (MR) of the ICP-SFMS to separate plutonium isotopes physically from interfering polyatomic species, and, on the other, use of a desolvation introduction system (DIS) to enhance sensitivity, thus partly compensating for the loss of transmission due to use of a higher resolution. Plutonium peaks are perfectly separated from the major interfering species (PbO 2, HgAr, and IrO 3) with a mass resolution of ~ 4000. The resulting nine-fold transmission loss is partly compensated by a five-fold increase in sensitivity obtained with the DIS and a lower background. The instrumental detection limits for plutonium isotopes, calculated for measurements of pure synthetic solutions, of the new method (known as MR-DIS method) and of the one currently used in the laboratory (LR method), based on a low mass resolution equal to 360, a microconcentric nebulizer and two in-line cooled spray chambers, are roughly equivalent, at around 0.2 fg ml − 1 . Regarding the measurement of real-life samples, the results obtained with both methods agree and the corresponding analytical detection limits for plutonium isotopes 239Pu, 240Pu and 241Pu are of a few fg·ml − 1 of sample solution, slightly lower with the MR-DIS method than with the current LR method. Although less sensitive than other plutonium ICP-MS measurement methods described in the literature, the main advantage of the MR-DIS method is that it is robust against the risk of false plutonium detection, even in the case of relatively high concentrations of heavy elements like lead, mercury or iridium.