Optimisation of plutonium separations using TEVA cartridges and ICP-MS/MS analysis for applicability to large-scale studies in tropical soils

Abstract

The analysis of plutonium (Pu) in soil samples can inform the understanding of soil erosion processes globally. However, there are specific challenges associated for analysis in tropical soils and so an optimal analytical methodology ensuring best sensitivity is critical. This method aimed to demonstrate the feasibility of sample preparation and analysis of Pu isotopes in African soils, considering the environmental and cost implications applicable to low-resource laboratories. The separation procedure builds upon previous work using TEVA columns, further demonstrating their usefulness for the reduction of uranium (U) interference in ICP-MS analysis with enhanced selectivity for Pu. Here several steps were optimised to enhance Pu recovery, reducing method blank concentration, and improving the separation efficiency through the determination of the elution profiles of U and Pu. The elimination of the complexing agent in the eluent, increased the spike recovery by improving matrix tolerance of the plasma, and simplified the separation procedure, improving throughput by 20%. The subsequent method was validated through the analysis of Certified Reference Material IAEA-384, where high accuracy and improved precision of measurement were demonstrated (measured value 114 ± 12 versus certified value 108 ± 13 Bq kg⁻¹). Optimisation of the column separation, along with the analysis of the samples using O₂ gas in ICP-MS/MS mode to mass shift Pu isotopes away from interfering molecular U ions provided a simple, robust, and cost-effective method with low achievable method detection limits of 0.18 pg kg^{−1 239+240}Pu, applicable to the detection of ultra-trace fallout Pu in African soils.