title: Tailored bifunctional polymer for plutonium monitoring.
abstract: Monitoring of actinides with sophisticated conventional methods is affected by matrix interferences, spectral interferences, isobaric interferences, polyatomic interferences, and abundance sensitivity problems. To circumvent these limitations, a self-supported disk and membrane-supported bifunctional polymer were tailored in the present work for acidity-dependent selectivity toward Pu(IV). The bifunctional polymer was found to be better than the polymer containing either a phosphate group or a sulfonic acid group in terms of (i) higher Pu(IV) sorption efficiency at 3-4 mol L(-1) HNO3, (ii) selective preconcentration of Pu(IV) in the presence of a trivalent actinide such as Am(III), and (iii) preferential sorption of Pu(IV) in the presence of a large excess of U(VI). The bifunctional polymer was formed as a self-supported matrix by bulk polymerization and also as a 1-2 μm thin layer anchored on a microporous poly(ether sulfone) by surface grafting. The proportions of sulfonic acid and phosphate groups in both the self-supported disk and membrane-supported bifunctional polymer were found to be the same as expected from the mole proportions of monomers in polymerizing solutions used for syntheses. α radiography by a solid-state nuclear track detector indicated fairly homogeneous anchoring of the bifunctional polymer on the surface of the membrane. Pu(IV) preconcentrated on a single bifunctional bead was used for determination of the Pu isotopic composition by thermal ionization mass spectrometry. The membrane-supported bifunctional polymer was used for preconcentration and subsequent quantification of Pu(IV) by α spectrometry using the absolute efficiency at a fixed counting geometry. The analytical performance of the membrane-supported-bifunctional-polymer-based α spectrometry method was found to be highly reproducible for assay of Pu(IV) in a variety of complex samples.
authors.affiliation: Fuel Chemistry Division, ‡Radiochemistry Division, and §Radiometallurgy Division, Bhabha Atomic Research Centre (BARC) , Trombay, Mumbai-400 085, India.
authors.forename: Sumana
authors.initials: S
authors.lastname: Paul
authors.forename: Ashok K
authors.initials: AK
authors.lastname: Pandey
authors.forename: Pranaw
authors.initials: P
authors.lastname: Kumar
authors.forename: Santu
authors.initials: S
authors.lastname: Kaity
authors.forename: Suresh K
authors.initials: SK
authors.lastname: Aggarwal
mesh_terms: D000327:Adsorption; D005591:Chemical Fractionation / Q000379:methods; D013058:Mass Spectrometry / Q000379:methods; D008567:Membranes, Artificial; D010710:Phosphates / Q000737:chemistry*; D011005:Plutonium / Q000032:analysis*; D011108:Polymers / Q000737:chemistry*; D016062:Porosity; D013450:Sulfones / Q000737:chemistry*; D013451:Sulfonic Acids / Q000737:chemistry*
chemical_list: D008567:Membranes, Artificial; D010710:Phosphates; D011108:Polymers; D013450:Sulfones; D013451:Sulfonic Acids; C022840:polyether sulfone; D011005:Plutonium