Vol 54, No 13 (2016)

In this paper, we consider the present-day situation and outlooks of the development of nuclear power generation in Russia and other countries. It was noted that the implementation of the concept of a closed nuclear-fuel cycle accepted in Russia relies on the solution of the problem of the disposal of spent nuclear fuel (SNF) and radioactive waste (RAW). This paper presents the main results of investigations focused on the development of radiation-safe methods of manufacturing nuclear fuel elements, including mixed uranium–plutonium oxide fuel for fast-neutron reactors; creation of low waste-production technologies of SNF processing and RAW disposal; and the analysis of fundamental features of the behavior and speciation of radionuclides in environmental objects for the development of efficient methods of radioecological monitoring and remediation of radionuclide-contaminated areas.

Large-scale melting of the Earth’s early mantle under the effect of global impact processes was accompanied by the generation of volatiles, which concentration was mainly controlled by the interaction of main N, C, O, and H gas-forming elements with silicate and metallic melts at low oxygen fugacity (fO₂), which predominated during metallic segregation and self-oxidation of magma ocean. The paper considers the application of Raman and IR (infrared) Fourier spectroscopy for revealing the mechanisms of simultaneous dissolution and relative contents of N, C, O, and H in glasses, which represent the quench products of reduced model FeO–Na₂O–Al₂O₃–SiO₂ melts after experiments at 4 GPa, 1550°C, and fO₂ 1.5–3 orders of magnitude below the oxygen fugacity of the iron—wustite buffer equilibrium (fO₂(IW)). Such fO₂ values correspond to those inferred for the origin and evolution of magma ocean. It was established that the silicate melt contains complexes with N–H bonds (NH₃, NH₂⁺, NH₂^-), N₂, H₂, and CH₄ molecules, as well as oxidized hydrogen species (OH^– hydroxyl and molecular water H₂O). Spectral characteristics of the glasses indicate significant influence of fO₂ on the N–C–O–H proportion in the melt. They are expressed in a sharp decrease of NH₂⁺, NH₂^-(O–NH₂), OH^–, H₂O, and CH₄ and simultaneous increase of NH₂^-(≡Si–NH₂) and NH₃ with decreasing fO₂. As a result, NH₃ molecules become the dominant nitrogen compounds among N–C–H components in the melt at fO₂ two orders of magnitude below fO₂(IW), whereas molecular СН₄ prevails at higher fO₂. The noteworthy feature of the redox reactions in the melt is stability of the ОН^– groups and molecular water, in spite of the sufficiently low fO₂. Our study shows that the composition of reduced magmatic gases transferred to the planet surface has been significantly modified under conditions of self-oxidation of mantle and magma ocean.

Researchers of the Vernadsky Institute of Geochemistry and Analytical Chemistry of the Russian Academy of Sciences created a luminescence photometer of a new generation for the determination of trace amounts of uranium and transuranium elements (TUE). The limits of detection for actinides vary from 0.3 pg for uranium and neptunium to 2.0 pg for plutonium. For ²³⁷Np, the relative limit of detection is 0.008 Bq/L. The photometer was tested in the radioecological monitoring of a number of polluted zones in Russia. The dynamics of actinide migration in all of the studied zones enhanced in the series ²³⁹Pu < ²⁴¹Am < ²³⁷Np. In this series, concentrations of radionuclides in water-soluble and exchange forms that are most mobile and determine the migration mobility of chemical elements increased in all of the studied soil types. In the group of fulvic acids, concentrations of radionuclides decreased in the series ²³⁷Np > ²⁴¹Am > ²³⁹Pu irrespectively of the soil. In the group of humic acids, concentrations of radionuclides increased in the series ²³⁷Np < ²³⁹Pu < ²⁴¹Am. The sorption coefficients of radionuclides by bottom sediments of the Markha River (Kraton-3 underground nuclear explosion site) and Lake Kyzyltash (East Urals Radioactive Trace) were calculated. Bioaccumulation factors of radionuclides by different plants in the impact area of the Kraton underground nuclear explosion were determined depending on the plant type.

The physical and mathematical models were used to study the method of acid retardation for separating acids from their salts in concentrated multicomponent solutions using nanoporous sorption materials. A combined mechanism of separation relies on the fact that in the sorption phase having a low dielectric permittivity, smaller-sized acid particles, namely, the molecules or strongly bound and weakly hydrated ion pairs, can penetrate the nanopores and are retained within these pores due to molecular sorption or competitive solvation forces. The dissolved salts presented by highly hydrated ions or weakly bound ion pairs can easily pass through the porous medium with a flow of concentrated solution, which is pumped through the column packed with the granulated bed of gel-type ion exchange resins or hypercrosslinked polymers. In conventional cyclic AR processes, purified acid is desorbed by water according to the mechanism of competitive solvation. However, such processes can be successfully used only when the salts separated from acids are highly soluble, as is the case with chloride and nitrate solutions free of components that may form compounds insoluble in neutral medium. At the separation in real sulfate and phosphate media, which normally contain alkaline earth metals and other components, conventional AR- based technologies proved to be unsuccessful. The new modified version of acid retardation is based on the previously discovered effect of stabilization of colloidal systems and supersaturated solutions in porous ion exchange media. A distinctive feature of the proposed technique is the use of weakly acidic aqueous solutions, instead of water, at the stages of acid displace in the cyclic AR processes. The proposed technique of WPA purification using strong-base gel-type ion exchangers in the phosphate form opens up the possibility of stable and feasible processes of acid separation and purification with simultaneous extraction of valuable components, e.g., REE concentrate.

A combined approach to the analysis of volcanic ash (VA) was proposed. Ash particles were separated by size using a combination of vibration sieving on sieves (140, 70, 40 μm) and field-flow fractionation in a rotating coiled column (for separation of nano- and submicron particles). Initial samples and obtained fractions were characterized using scanning electron microscopy and static light scattering. Their elemental composition was determined using ICP-MS and ICP-AES methods. The radionuclide composition of the VA was studied by the low-background gamma spectrometry. The studies were carried out by the example of ashes from Puyehue volcano, the Puyehue Cordón Caulle volcanic group, Andes (Santiago, eruption on June, 2011), which were taken immediately after eruption and after first rain. It was shown that up to 15% of major elements (such as P, Ca, and К) and trace elements (such as Be, Hg, Tl, As, Sb, and Bi) could be extracted from the ash by rain and migrate into environment. It was also found that the content of radionuclides (U²³⁵, Th²³⁴, Pb²¹⁴, Bi²¹⁴, Be⁷) after rain decreases by 30–40%. Of special interest are ash nanoparticles (up to 200 nm), in which the contents of Cu, Pb, Tl, Bi, Sn, As, and Sb are over an order of magnitude higher than the bulk contents of these elements in the ash. This regularity was found in samples taken both prior to and after rain. The proposed methodology of fractionation, study, and analysis of ash particles may be applied for a wide range of soil, ash, and dust samples of different nature.