Aqueous Complexation of Thorium(IV), Uranium(IV), Neptunium(IV), Plutonium(III/IV), and Cerium(III/IV) with DTPA

Aqueous complexation of Th(IV), U(IV), Np(IV), Pu(III/IV), and Ce(III/IV) with DTPA was studied by potentiometry, absorption spectrophotometry, and cyclic voltammetry at 1 M ionic strength and 25 °C. The stability constants for the 1:1 complex of each trivalent and tetravalent metal were calculated. From the potentiometric data, we report stability constant values for Ce(III)DTPA, Ce(III)HDTPA, and Th(IV)DTPA of log β₁₀₁ = 20.01 ± 0.02, log β₁₁₁ = 22.0 ± 0.2, and log β₁₀₁ = 29.6 ± 1, respectively. From the absorption spectrophotometry data, we report stability constant values for U(IV)DTPA, Np(IV)DTPA, and Pu(IV)DTPA of log β₁₀₁ = 31.8 ± 0.1, 32.3 ± 0.1, and 33.67 ± 0.02, respectively. From the cyclic voltammetry data, we report stability constant values for Ce(IV) and Pu(III) of log β₁₀₁ = 34.04 ± 0.04 and 20.58 ± 0.04, respectively. The values obtained in this work are compared and discussed with respect to the ionic radius of each cationic metal

Microstructure damage of titanium films by irradiation with fission fragments

Radiation damage caused by fission fragments to metal surfaces is an important research topic. Thin titanium foils were irradiated with a continuous wave beam of 132 MeV ¹³²Xe+²⁹ at the current intensity of 2 pnA. Pre- and post-irradiated surface topologies were investigated using atomic force microscopy and the observed defects were quantified by root mean square roughness, depth profile of the disordered zones, size and areal density of the voids, and discussed as a function of the applied fluencies (1– 9) 10¹³ Xe/cm². The first ellipsoidal dislocation loops appeared at the fluence of 3.0 10¹³ Xe/cm² with the areal density of 1.56 10⁶/cm² that increased to 2.0 10⁷ cm ⁻² when the dose rose to 9.0 10¹³ Xe/ cm2. At this point also the first dislocation lines with the density of 1.3 10⁷ cm ⁻² were seen. Our results suggest that the fission fragments might maximize large voids and dislocations and increase the degradation in depth resolution.Keywords: Voids, Dislocation lines, Dislocation loop, Titanium, Radiation damag

Development of scalable and versatile nanomaterial libraries for nanosafety studies: polyvinylpyrrolidone (PVP) capped metal oxide nanoparticles

The potential long-term environmental impact of manufactured nanomaterials (NMs) remains poorly understood, and the need to better predict NM fate and transformations and chronic effects is particularly urgent. Compared to their bulk counterparts, manufactured NMs can have distinct physical and chemical characteristics, which influence their behaviour, stability and toxicity. It is therefore essential to develop standard and reference NM libraries for environmental nanoscience and nano(eco)toxicology, and to facilitate a move towards computational prediction of NM fate, through quantitative structure–activity relationships for example. The aim of this work was to develop and fully characterise one such library, which included comparable NMs with a range of core chemistries, but the same capping agent and size range, for use in future studies to test the hypothesis that the core chemistry is a primary factor in controlling toxicity. The library contained the following NMs: 10k, 40k and 360k PVP capped ceria, zinc oxide and copper oxide (9 NMs in total). The work presented here upholds the underpinning hypothesis that the mechanism of NM formation is the same in all cases, suggesting that the protocol is very robust and has the potential to generate a wide range of comparable metal oxide NMs and potentially expand the library further with doped metal oxide and metal NMs. Characterisation by means of DLS (both size and zeta measurements), UV/Vis, XPS, FT-IR, TEM, STEM, EDX and EELS confirms that the tested synthesis protocol can easily and successfully be used to create stable PVP capped metal oxide NMs of reproducible sizes

Reduction of Np(VI) in Irradiated Solutions of Nitric Acid

The reliable separation of neptunium from dissolved nuclear fuel assumes the ability to maintain a preferred oxidation state. However, regardless of its initial redox speciation, a series of reactions occurs in nitric acid to create a mixture of oxidation states including Np(V), Np(VI) and sometimes Np(IV). To further complicate the situation, irradiated solutions such as fuel dissolution contain both transient and long-lived radiolysis products which may be strongly oxidizing or reducing. Thus, irradiation may be expected to impact the equilibrium distributions of the various neptunium valences. Among the transient products of the irradiation of aqueous nitric acid are the reducing •H atom and solvated electron (e-aq) and the oxidizing •OH radical from water radiolysis, and the oxidizing •NO3 and •NO2 radicals from nitric acid radiolysis. Longer-lived radiolysis products include hydrogen peroxide from water radiolysis and nitrous acid from nitric acid radiolysis. It has long been known that HNO2 acts as a reducing agent toward Np(VI); however, the effects of the oxidizing transient species have been less well studied. Here we have irradiated nitric acid solutions of neptunium with 60Co gamma-rays, and measured radiolytically-induced changes in neptunium valences, as well as the nitrous acid concentration, by UV/Vis spectroscopy. It was found that in 4M HNO3 at low absorbed doses, the oxidizing radicals oxidized Np(V) to Np(VI). However, as the irradiation proceeded the concentration of nitrous acid became sufficient to reduce Np(VI) to Np(V), and then continued irradiation favored this reduction until an equilibrium was achieved in balance with the oxidation of Np(V) by nitric acid itself. The starting abundances of the two neptunium valences did not affect the final equilibrium concentrations of Np(V) and Np(VI), and no Np(IV) was detected

The use of electrolyte redox potential to monitor the Ce(IV)/Ce(III) couple

Mathematical modelling of the oxidation reduction redox potential (ORP) of an electrolyte has been carried out for a batch system comprising an electrochemical reactor and an electrolyte circuit containing a redox couple. The ORP can be useful to monitor the environmental impact of chemical species in solution that represent a risk to the environment. Considerations of four fundamental equations, namely, the Nernst equation, a mass balance, Faraday's laws of electrolysis and a first order kinetic equation, leads to an expression for the electrolyte redox potential as a function of the batch time, the electrical charge and the redox concentration. Such an expression facilitates graphical plots which can be used to estimate kinetic parameters, current efficiency and the relative redox concentration. The Ce(IV)/Ce(III) system has been chosen as a model reaction for electrolyte redox potential measurement in a batch recycle system consisting of a pumped flow through a divided FM01-LC parallel plate electrochemical reactor (64 cm2 projected electrode area) and a well mixed tank (3,600 cm3). The differences between experimental and model predictions are discussed

Aqueous Complexation of Thorium(IV), Uranium(IV), Neptunium(IV), Plutonium(III/IV), and Cerium(III/IV) with DTPA

Aqueous complexation of Th­(IV), U­(IV), Np­(IV), Pu­(III/IV), and Ce­(III/IV) with DTPA was studied by potentiometry, absorption spectrophotometry, and cyclic voltammetry at 1 M ionic strength and 25 °C. The stability constants for the 1:1 complex of each trivalent and tetravalent metal were calculated. From the potentiometric data, we report stability constant values for Ce­(III)­DTPA, Ce­(III)­HDTPA, and Th­(IV)­DTPA of log β₁₀₁ = 20.01 ± 0.02, log β₁₁₁ = 22.0 ± 0.2, and log β₁₀₁ = 29.6 ± 1, respectively. From the absorption spectrophotometry data, we report stability constant values for U­(IV)­DTPA, Np­(IV)­DTPA, and Pu­(IV)­DTPA of log β₁₀₁ = 31.8 ± 0.1, 32.3 ± 0.1, and 33.67 ± 0.02, respectively. From the cyclic voltammetry data, we report stability constant values for Ce­(IV) and Pu­(III) of log β₁₀₁ = 34.04 ± 0.04 and 20.58 ± 0.04, respectively. The values obtained in this work are compared and discussed with respect to the ionic radius of each cationic metal