Rapid determination of plutonium isotopes in small samples using single anion exchange separation and ICP-MS/MS measurement in NH₃–He mode for sediment dating

To accurately determine ultra-trace Pu isotopes in small environmental samples, we explored ICP-MS/MS in NH3–He mode, and investigated mechanism of 238U interference removal and measurement sensitivity improvement for plutonium isotopes. The interference of uranium and uranium hydrides was effectively eliminated using 0.4 mL/min NH3 as reaction gas by shifting them to U(NHm)n+ and UH(NHm)n+.

The overall interference of uranium was reduced to <2.4 × 10−7, while remaining excellent 239Pu sensitivity (13,900 Mcps/(mg/L)) mainly due to ion focusing effect of Pu by helium gas. On this basis, the purification of plutonium using a single AG1- × 4 column was proved to be sufficient for accurate determination of plutonium isotopes by the developed detection method, and the detection limits for the method were estimated to be 0.16 fg (0.4 μBq) for 239Pu, 0.046 fg (0.4 μBq) for 240Pu and 0.039 fg (0.15 mBq) for 241Pu.

The method was validated by analyzing plutonium isotopes in certificated reference materials and reported environmental samples of only 1–2 g. The analytical results of ultra-trace Pu isotopes in small amounts (∼1 g) of lake sediments obtained by the developed method were successfully applied to sediment dating