The characterisation by luminescence spectroscopy of uranium(VI) incorporated into zeolites and aluminas

Luminescence spectroscopy of solids at 77 K has been used to characterise the uranium(VI) species incorporated into [alpha]-alumina, [gamma]-alumina and zeolites Y and ZSM-20 by adsorption from solution and into ZSM-5 by chemical synthesis. With uranyl adsorbed from nitrate solutions onto [alpha]- and [gamma]-aluminas, the luminescence measurements show the dominant uranium species is schoepite, UO3·xH2O, in agreement with results from X-ray diffraction and Raman spectroscopy. With uranyl acetate, there are indications that a crystalline acetate species is also present. With zeolite-Y and ZSM-20, the main species is a dimer. In addition, some monomeric [UO2(H2O)5]2+ is also present. With ZSM-5, although this is not observed in X-ray diffraction, the luminescence spectrum shows the presence of a species, similar to the schoepite seen with the aluminas. It is suggested that this may be due both to closely related polymeric species, and to uranyl anions, such as [UO2(OH)4]2- and [UO2(OH)3]-.http://www.sciencedirect.com/science/article/B6TGS-435M5SD-2D/1/1fcff58939e013c8fdee4bba2d901a3

The characterisation by luminescence spectroscopy of uranium(VI) incorporated into zeolites and aluminas

Luminescence spectroscopy of solids at 77 K has been used to characterise the uranium(VI) species incorporated into [alpha]-alumina, [gamma]-alumina and zeolites Y and ZSM-20 by adsorption from solution and into ZSM-5 by chemical synthesis. With uranyl adsorbed from nitrate solutions onto [alpha]- and [gamma]-aluminas, the luminescence measurements show the dominant uranium species is schoepite, UO3·xH2O, in agreement with results from X-ray diffraction and Raman spectroscopy. With uranyl acetate, there are indications that a crystalline acetate species is also present. With zeolite-Y and ZSM-20, the main species is a dimer. In addition, some monomeric [UO2(H2O)5]2+ is also present. With ZSM-5, although this is not observed in X-ray diffraction, the luminescence spectrum shows the presence of a species, similar to the schoepite seen with the aluminas. It is suggested that this may be due both to closely related polymeric species, and to uranyl anions, such as [UO2(OH)4]2- and [UO2(OH)3]-.http://www.sciencedirect.com/science/article/B6TGS-435M5SD-2D/1/1fcff58939e013c8fdee4bba2d901a3

Evaluation of the LDPM elastic and fracture parameters by up-scaling procedure

The heterogeneity of the concrete may be considered on different size scales of observation, ranging from the atomistic scale (10-10m), characterized by the behavior of crystalline particles of hydrated Portland cement, to the macroscopic scale (101 m), where concrete has traditionally been considered homogeneous. The multiscale framework we are proposing in this paper is based on the following models: chemical analyses at the cement paste scale; mechanical lattice model at the cement and mortar scales; geometrical aggregate distribution models at the mortar and concrete scales; and the Lattice Discrete Particle Model (LDPM) at the concrete scale. For that purpose, a set of analysis starting from a known set of parameters of the cement paste. This input is utilized to evaluate the mechanical properties of the mortars (cement and sand), and then these properties are used to evaluate the mechanical properties of the mortar-a4 (mortar-s and aggregate smaller then 4mm). The upscaling in the proposed methodology involved the evaluation of the LDPM concrete parameters based on the mortara4 properties. Here we are suggesting a uni-axial tension "numerical experiments" on the mortar-a4 scale to evaluate the elastic and fracture LDPM mechanical parameters

Electron-Transfer Oxidation of Chlorophenols by Uranyl Ion Excited State in Aqueous Solution. Steady-State and Nanosecond Flash Photolysis Studies

The oxidation of chlorophenols by photoexcited uranyl ion was studied in aqueous solution at concentrations where the ground-state interactions were negligible. Nanosecond flash photolysis showed that a clean electron-transfer process from the chlorophenols to the excited uranyl ion is involved. This is suggested to lead to the formation of a U(V)/chlorophenoxyl radical pair complex. The efficiency of this charge-transfer process is unity for the three chlorophenols. However, low product yields suggest that in the absence of oxygen, back electron transfer, both within the radical pair and from separated uranium(V) to phenoxyl radicals, appears to be the major reaction pathway. In the presence of oxygen the quantum yields of disappearance of chlorophenol and of photoproduct formation increased. This leads to the conclusion that oxygen favors reaction with uranium(V) and/or the uranium(V)−phenoxyl radical pair, leading to the formation of the superoxide anion and its conjugate acid, HO2•, which then regenerate UO22+. Based on this, a catalytic cycle for chlorophenol photooxidation involving uranyl ion and molecular oxygen is proposed

Aqueous solutions of uranium(VI) as studied by time-resolved emission spectroscopy: A round-robin test

Results of an inter-laboratory round-robin study of the application of time-resolved emission spectroscopy (TRES) to the speciation of uranium(VI) in aqueous media are presented. The round-robin study involved 13 independent laboratories, using various instrumentation and data analysis methods. Samples were prepared based on appropriate speciation diagrams and, in general, were found to be chemically stable for at least six months. Four different types of aqueous uranyl solutions were studied: (1) acidic medium where UO2aq2+ is the single emitting species, (2) uranyl in the presence of fluoride ions, (3) uranyl in the presence of sulfate ions, and (4) uranyl in aqueous solutions at different pH, promoting the formation of hydrolyzed species. Results between the laboratories are compared in terms of the number of decay components, luminescence lifetimes, and spectral band positions. The successes and limitations of TRES in uranvl analysis and speciation in aqueous solutions are discussed

Aqueous solutions of Uranium (VI) as studied by time-resolved emission spectroscopy: a round-robin test

Results of an inter-laboratory round-robin study of the application of time-resolved emission spectroscopy (TRES) to the speciation of uranium(VI) in aqueous media are presented. The round-robin study involved 13 independent laboratories, using various instrumentation and data analysis methods. Samples were prepared based on appropriate speciation diagrams and, in general, were found to be chemically stable for at least six months. Four different types of aqueous uranyl solutions were studied: (1) acidic medium where UO2 21 aq is the single emitting species, (2) uranyl in the presence of fluoride ions, (3) uranyl in the presence of sulfate ions, and (4) uranyl in aqueous solutions at different pH, promoting the formation of hydrolyzed species. Results between the laboratories are compared in terms of the number of decay components, luminescence lifetimes, and spectral band positions. The successes and limitations of TRES in uranyl analysis and speciation in aqueous solutions are discussed