Hybrid extractive scintillator resin for simultaneous concentration and detection of plutonium from aqueous solutions.

A scoping study of a commercially available resin selective for aqueous plutonium (Pu), AnaLig® Pu-02, modified with scintillator was investigated as a scheme to simultaneously concentrate and detect Pu in aquatic matrices. The extractive scintillating resin was comprised of a silica base, functionalized for plutonium extraction, grafted with plastic scintillator of polyvinyl toluene (PVT) and 2-(1-naphthyl)-4-vinyl-5- phenyloxazole (vNPO) fluor. Scintillator was incorporated onto the AnaLig® Pu-02 resin in a two-step process of silanization followed by surface-polymerization. Successful modification was facilitated by grinding the resin beads prior to silanization to expose cleaved silica surface sites appropriate for scintillator grafting. The modified resin was subjected to initial characterization of batch uptake and radioluminosity measurements where a total detection efficiency of 32.5% was observed. The modified resin was then subjected to pH 1 simulants containing environmental relevant groundwater constituents of varying concentration. Concentrations of 0.001M Fe(III) interfered with Pu uptake, while concentrations of up to 0.01M Ca(II) and 0.001 mM concentration of natural uranium and thorium had minimal influence on plutonium uptake. A translucent column packed with the modified AnaLig® Pu-02 was placed in a commercial flow-cell radiation detector for real-time detection of plutonium; a total detection efficiency of 20.4% was achieved for on-line measurements. The modification of AnaLig® Pu-02 results in a minimum detection limit capable of meeting the EPA limit for gross alpha activity in drinking water given a sufficient counting time of 15 min and approximately 300 mL of solution volume.

Hybrid extractive scintillator resin for simultaneous concentration and detection of radiocesium from aqueous solutions.

A hybrid extractive scintillating resin (HESR) was developed for the concentration and detection of radiocesium. The HESR comprised a cesium-selective potassium ferrierite ion-exchange powder embedded in porous polymeric scintillating beads. It was prepared by carrying out suspension polymerization of 4-methylstyrene with divinylbenzene, 2-(1-naphthyl)-4-vinyl-5-phenyloxazole fluor and ferrierite-K powder. A translucent column packed with the HESR was placed in a commercial flow-cell radiation detector for real-time detection of radiocesium. Measurements using the HESR detection system were compared with an on-line gamma-ray measurement using a NaI:Tl well detector containing a column of ferrierite-K powder/SiO2 or potassium-nickel ferrocyanate-polyacrylonitrile (KNiFC-PAN). The NaI:Tl well detector configuration quantified the gamma-ray from 137mBa, while the flow-cell detector primarily quantified the beta particles and conversion electrons of 137Cs. The minimum detectable concentration of the two detection modalities were calculated and shown to be lower than the maximum contaminant level in drinking water of 7.4 Bq/L (200 pCi/L).

Increase in the reduction potential of uranyl upon interaction with graphene oxide surfaces.

Coordination of uranyl (U(vi)) with carboxylate groups on functionalized graphene oxide (GO) surfaces has been shown to alter the reduction potential of the sorbed uranium ion. A quantitative measure of the reduction potential and qualitative estimation of sorption/desorption processes were conducted using cyclic voltammetry, and the proposed coordination environment was determined using the surface sensitive attenuated total reflection mode of infrared spectroscopy (ATR-FTIR). GO is a nanostructured material possessing a large amount of oxygen-containing functional groups both on basal planes and at the edges, which can form strong surface complexes with radionuclides. The presence of these functional groups on the surface of GO allows efficient immobilization of uranium due to sorption of uranyl (UO22+) to carboxylate, hydroxide, or sulfonate functional groups and the potential for enhanced reduction of U(vi) to more strongly sorbing and insoluble U(iv). Herein, binding of U(vi) to carboxylate groups on the GO surface is proposed as the primary sorption mechanism based on the FTIR study. Furthermore, the coordination of uranium with the surface increases the reduction potential of the U(vi)/U(iv) redox couple as compared to the case of the aqueous U(vi)/U(iv) species. This is consistent with the alteration of the electronic structure of the sorbed ion, which can be determined in our case due to the use of a GO-coated working electrode. Thus, GO-coated glassy carbon electrodes and other semi-conducting electrodes with high ion sorption capacities may provide a means of examining the oxidation/reduction potentials of sorbed ions.

Atomic force and ultrasonic force microscopy investigation of adsorbed layers formed by two incompatible polymers: polystyrene and poly(butyl methacrylate).

Atomic force microscopy (AFM) and ultrasonic force microscopy (UFM) have been used to study the properties of adsorption layers formed by two incompatible polymers, polystyrene and poly(butyl methacrylate), in the course of simultaneous adsorption on the surface of silica (naturally oxidized surface of a silicon wafer). The adsorption was performed from solutions containing both of the components in a common solvent (carbon tetrachloride) in dilute and semidilute concentration regimes. It was discovered that in both cases the structure of adsorption layers has a complex mosaic structure, the details of which depend on solution composition, on the solution concentration regime, and on the ratio of the components in the adsorption layer. The observed structural inhomogeneity on the length scale of approximately 200-500 nm (distribution of segment density revealed by UFM) appears as result of thermodynamic incompatibility in the system and is conditioned by changes in the conformation states of the adsorbed macromolecules in the route of competitive adsorption of the components. The adsorbed polymer films with thicknesses of approximately 20-500 nm appeared to have fractal properties and could be characterized with fractal dimensions dependent on the ratio of the components at the interface and the adsorption conditions.

Micro orientation and anisotropy of conductivity in liquid crystalline polymer films filled with carbon nanotubes.

In this communication we report the preferential orientation of single wall carbon nanotubes (SWNT) in a nematic liquid crystalline (LC) polymer matrix. The alignment of the nanotubes was characterized through anisotropy of electrical conductivity of the composite measured in directions parallel and perpendicular to the nematic director. The anisotropy of the nanocomposite films strongly depends on the nanotube concentration in the range from 1 to 10% and vanished at higher loads. The electrical conductivity of nanocomposites is related to their structural features revealed by atomic force microscopy and Raman spectroscopy experiments and is explained by a strong coupling between the nanotubes and the polymer matrix.