Search

The radiolytic behaviors of aqueous ammonia solutions under γ-ray irradiation were investigated, focusing on several factors, including initial ammonia concentration, absorbed dose, and H3BO3 concentration. The main species including ammonia, H2O2, nitrogen oxides, and H2, were quantitatively analyzed. The results revealed the significant influence of the initial ammonia concentration on the radiolytic behavior of the aqueous ammonia solution. The existence of ammonia in the solution exhibited suppression of the concentrations of H2O2 and O2. Furthermore, the radiolysis of aerated aqueous ammonia solution led to the formation of nitrogen oxides (NO2− and NO3−). This process was driven by multiple oxidation reactions, in which O2 and ·OH played crucial roles. Interestingly, the addition of H3BO3 provided protection to ammonia during γ irradiation, while the concentration of H2O2 was increased. [ABSTRACT FROM AUTHOR]

γ-raysand pulse radiolysis of aqueous solutions of Ni2+ionsin the presence of polyacrylate (PA–) and 2-propanolleads to the formation of metastable species absorbingat 540 nm that are ascribed to “pink” oligomeric clustersof a few nickel atoms only. The molar absorption coefficient is evaluatedas ε540 nm= 3300 ± 300 L mol–1cm–1per Ni0atom. The successive stepsfrom the reduction of Ni2+into Ni+ions tothe formation of the pink clusters at 540 nm under conditions of complexationby PA–are investigated by pulse radiolysis. Theyield of the formation of pink clusters increases markedly with theirradiation dose rate, demonstrating the occurrence of the disproportionationof the [Ni+, PA–] complex after a singleelectron pulse. The reduction and nucleation mechanisms, includingrate constants, in competition with the back oxidation by protons,particularly at low dose rate, are discussed. [ABSTRACT FROM AUTHOR]

The radiation-induced reactions of a water-soluble coumarin derivative, coumarin-3-carboxyl acid (C3CA), have been investigated in aqueous solutions by pulse radiolysis with a 35 MeV electron beam, final product analysis following 60Co γ-irradiations and deterministic model simulations. Pulse radiolysis revealed that C3CA reacted with both hydroxyl radicals (•OH) and hydrated electrons (e− aq) with near diffusion-controlled rate constants of 6.8 × 109 and 2.1 × 1010 M−1 s−1, respectively. The reactivity of C3CA towards O2• − was not confirmed by pulse radiolysis. Production of the fluorescent molecule, 7-hydroxy-coumarin-3-carboxylic acid (7OH-C3CA), was confirmed by final product analysis with a fluorescence spectrometer coupled to a high performance liquid chromatography (HPLC) system. Production yields of 7OH-C3CA following 60Co γ-irradiations depended on the irradiation conditions and ranged from 0.025 to 0.18 (100 eV) −1. Yield varied with saturating gas, additive and C3CA concentration, implying the presence of at least two pathways capable of providing 7OH-C3CA as a stable product following the scavenging reaction of C3CA with •OH, including a peroxidation/elimination sequence and a disproportionation pathway. A reaction mechanism for the two pathways was proposed and incorporated into a deterministic simulation, showing that the mechanism can explain experimentally measured 7OH-C3CA yields with a constant conversion factor of 4.7% from •OH scavenging to 7OH-C3CA production, unless t-BuOH was added. [ABSTRACT FROM AUTHOR]

Solvatochromic shift of 4,4′-bpyH in aqueous solutions at elevated temperatures up to supercritical conditions and in various organic solvents with different dielectric constants, is investigated by pulse-radiolysis technique. 4,4′-bpyH shows a stronger solvent–solute interaction in water than in organic solvents, perhaps due to the hydrogen bond between 4,4′-bpyH and water. At 380 °C, local density augmentation, namely ρ local – ρ bulk , in supercritical water becomes 280 kg m −3 ( ρ bulk = 208 kg m −3 ), and the density enhancement factor is 8.9. Density fluctuation maximizes when ρ bulk is around 120 kg m −3 . Density inhomogeneity decreases as temperature rises, but is still remarkable at 400 °C. [ABSTRACT FROM AUTHOR]

• An acetone-enhanced photoreduction method was adopted to separate ReO 4 −. • The mechanism of enhanced photoreduction by acetone was proposed. • The efficient separation (separation ratio > 95.2%) of Re was achieved within 30 min. • The selective photoreduction separation of Re(VII) / Nd(III) was realized. Efficient separation of rhenium (Re) from aqueous solution is pivotal in the resource recovery, and suitable to simulate the elimination of radiotoxic technetium (Tc) due to their similar properties. In this work, we achieved a high Re(VII) separation ratio of 95.2% within 30 min from aqueous solution via an acetone-enhanced photoreduction method, in which soluble ReO 4 − was reduced to insoluble ReO x and Re(0) in the presence of acetone and isopropanol. Compared with the situation in absence of acetone, acetone absorbed most of the UV energy, and the produced triplet acetone could abstract H α atoms from isopropanol to form more strongly reductive ketyl radicals, leading to the enhancement in photoreduction. Isopropanol was the most qualified for Re(VII) photoredction due to its low C–H α bond energy. The addition of alkali also benefited the Re(VII) separation by eliminating produced protons, and stabilizing the intermediate Re(VI) to preventing the re-formation of Re(VII) through disproportionation of Re(VI). Furthermore, selective and effective separation of Re(VII) from simulated high level liquid waste containg Nd(III) was realized as well. This work gains an insight into the role of acetone in the enhanced Re(VII) photoreduction, which may be of great significance in developing novel approaches for hydrometallurgy and spent nuclear fuel reprocessing. [ABSTRACT FROM AUTHOR]