Determination of Femtogram-Level Plutonium Isotopes in Environmental and Forensic Samples with High-Level Uranium Using Chemical Separation and ICP-MS/MS Measurement

摘要

ICP-MS is becoming a competitive technique for measurement of plutonium isotopes. Besides the abundance sensitivity (tailing of U-238 to m/z = 239 and 240), isobaric and polyatomic ions interferences (e.g., (UH+)-U-238-H-1) are the most critical challenges for determination of low-level plutonium in high uranium samples. This work presents a new method to solve this problem using ICP-MS with two tandem quadrupole separators and a dynamic collision/reaction cell combined with chemical separation. The interference of uranium hydrides ((UH+)-U-238-H-1 and (UH2+)-U-238-H-1) was effectively eliminated using CO2 as reaction gas by converting hydrides to oxides of uranium ions (UO+/UO2+) but still keeping the intensity of the Pu+ signal. The tailing interference of U-238(+) (abundance sensitivity) was intensively eliminated by significantly suppressing the U-238(+) signal using CO2 as reaction gas and using two tandem quadrupole mass separators in the ICP-MS/MS. With these approaches the overall interference of uranium was reduced to <1 x 10(-8), which is 3 orders of magnitude better than the conventional ICP-MS. Combined with chemical separation with a decontamination factor of 10(5) for uranium, an overall factor of 10(12) for elimination of uranium interference was achieved. The developed method was demonstrated to enable accurate determination of <10(-15) g/g level plutonium isotopes in environmental samples even in a uranium debris sample with a U/Pu atomic ratio of up to 10(12). The developed method was validated by analysis of a spiked solution and certified reference materials of soil.