title: Chemically selective polymer substrate based direct isotope dilution alpha spectrometry of Pu.
abstract: Quantification of actinides in the complex environmental, biological, process and waste streams samples requires multiple steps like selective preconcentration and matrix elimination, solid source preparations generally by evaporation or electrodeposition, and finally alpha spectrometry. To minimize the sample manipulation steps, a membrane based isotope dilution alpha spectrometry method was developed for the determination of plutonium concentrations in the complex aqueous solutions. The advantages of this method are that it is Pu(IV) selective at 3M HNO3, high preconcentration factor can be achieved, and obviates the need of solid source preparation. For this, a thin phosphate-sulfate bifunctional polymer layer was anchored on the surface of microporous poly(ethersulfone) membrane by UV induced surface grafting. The thickness of the bifunctional layer on one surface of the poly(ethersulfone) membrane was optimized. The thickness, physical and chemical structures of the bifunctional layer were studied by secondary ionization mass spectrometry (SIMS), scanning electron microscopy (SEM) and SEM-EDS (energy-dispersive spectroscopy). The optimized membrane was used for preconcentration of Pu(IV) from aqueous solutions having 3-4M HNO3, followed by direct quantification of the preconcentrated Pu(IV) by isotope dilution alpha spectrometry using (238)Pu spike. The chemical recovery efficiency of Pu(IV) was found to be 86±3% below Pu(IV) loading capacity (1.08 μg in 2×1 cm(2)) of the membrane sample. The experiments with single representative actinides indicated that Am(III) did not sorb to significant extent (7%) but U(VI) sorbed with 78±3% efficiency from the solutions having 3M HNO3 concentration. However, Pu(IV) chemical recovery in the membrane remained unaffected from the solution containing 1:1000 wt. proportion of Pu(IV) to U(VI). Pu concentrations in the (U, Pu)C samples and in the irradiated fuel dissolver solutions were determined. The results thus obtained were found to be in good agreement with those obtained by conventional alpha spectrometry, biamperometry and thermal ionization mass spectrometry.
authors.affiliation: Fuel Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India. Electronic address: sumana@barc.gov.in.
authors.forename: Sumana
authors.initials: S
authors.lastname: Paul
authors.affiliation: Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India.
authors.forename: Ashok K
authors.initials: AK
authors.lastname: Pandey
authors.affiliation: Fuel Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India.
authors.forename: R V
authors.initials: RV
authors.lastname: Shah
authors.affiliation: Fuel Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India. Electronic address: skaggr2002@gmail.com.
authors.forename: S K
authors.initials: SK
authors.lastname: Aggarwal
mesh_terms: D007201:Indicator Dilution Techniques; D013058:Mass Spectrometry / Q000379:methods; D008567:Membranes, Artificial; D011005:Plutonium / Q000032:analysis*; D011108:Polymers / Q000737:chemistry*; D016062:Porosity
chemical_list: D008567:Membranes, Artificial; D011108:Polymers; D011005:Plutonium
keywords: Alpha spectrometry; Dissolver solutions; Isotope dilution; Membrane; Plutonium(IV) selective; Surface grafting