Sorption of the Main Dose-forming Radionuclides of Nuclear Power Plants Drain Water on Natural Bentonite in the Process of their Co-ozonation

B. H. Shabalin¹, K. K. Yaroshenko¹,
O. M. Lavrynenko^{1, 2}, O. V. Marinich³, N. B. Mitsiuk¹

¹ SI “The Institute of Environmental Geochemistry of the National Academy of Sciences of Ukraine”, 34а, Palladina ave.,
Kyiv, 03142, Ukraine
² I. M. Frantsevich Institute for Problems of Materials Science of the National Academy of Sciences of Ukraine, 3,
Khrzhyzhanovskyi st., Kyiv, 03142, Ukraine
³ SI “Radioenviromental Centre of the National Academy of Sciences of Ukraine”, 55b, O. Honchara st., Kyiv, 01054, Ukraine

DOI: doi.org/10.31717/2311-8253.22.2.3

Abstract

The article presents the general pattern of the combined process of oxidative decomposition of organic components of simulated nuclear power plant (NPP) drain water and sorption interaction of the imitators of main dose-forming radionuclides (Cs – radiolabel for ¹³⁷Cs; stable isotopes of Co, Sr, Mn salts) on natural bentonites from the Cherkasy deposit in presence of sorption-reagent compounds — iron (II) and manganese (II) salts. Hydroxides, oxyhydroxides and oxides of Fe and Mn formed during ozonation are predominantly localized on the surface of bentonite. The chemical composition of the main elements of bentonite after drain water ozonation with the addition of iron and manganese salts remains almost the same as that of natural bentonite. The phase composition of bentonite is presented by the main rock-forming mineral montmorillonite and secondary mineral quartz. The iron-containing phases of the ozonised bentonite are Fe(II)- Fe(III) layered double hydroxides (Green Rust), goethite α-FeOOH and magnetite Fe₃O₄, and the manganese-containing phases are hausemannite Mn₃O₄, manganese oxide (II) and manganese oxyhydroxide MnO(OH)₂. The iron- and manganese-containing phases deposited on the bentonite surface during ozonation are predominantly weakly crystallized or amorphized structures. At the concentration of salts of iron (50 mg/dm³) and manganese (100 mg/dm³) in the drain water, the specific surface area of bentonites with the formed layer of iron and manganese hydroxides, (oxy)hydroxides and oxides increases compared to natural bentonite (34.2 m²/g) and equals to 55 and 51 m²/g, respectively. The degree of radionuclide removal during ozonationof the simulated solution with the initial concentration of cations (Fe²⁺ — 5 mg/dm³; Mn²⁺ —10 mg/dm³; Ca²⁺ — 5 mg/dm³) in the presence of natural bentonite is ¹³⁷Cs — 78% ± 2%, Sr²⁺ —97.55% ± 1%, Co²⁺ — 96.5% ± 1%, Mn²⁺ — 99.7% ± 0.5%. To preserve the efficiency of ¹³⁷Cs and Co²⁺ radionuclide removal, the initial concentration of cations in the solution can be increased to the following values: Fe²⁺ — 50 mg/dm³, Mn²⁺ — 100 mg/dm³, Ca²⁺ — 50 mg/dm³, and to: Fe²⁺ —500 mg/dm³, Mn²⁺ — 1,000 mg/dm³, Ca²⁺ — 500 mg/dm³ for Sr²⁺ and Mn²⁺ removal.

Keywords: NPP drain water, ozonolysis, sorption, doze-forming radionuclides, bentonite

References

1. Management of radioactive waste during operation of NPP. Report 2016. Kyiv: NNEGC “Energoatom”, 137 p. (in Ukr.)

2. Klyuchnikov A. A., Pazukhin E. M., Shygera Yu. M. (2005). Radioaktivnyye otkhody AES i metody obrashcheniya s nimi [Radioactive waste of NPPs and ways of their management]. Kyiv: ISP NPP, NAS of Ukraine, 487 p. (in Rus.)

3. Batiukhnova O. G., Bergman K., Efremenkov V. M., et al. (2005). Tekhnologicheskiye i organizatsionnyye aspekty obrashcheniya s radioaktivnymi otkhodami: seriya uchebnykh kursov [Technological and organizational aspects of radioactive waste management: a series of training courses]. Vienna: IAEA, 230 p. (in Rus.)

4. Savkin A. E. (2011). [Development and testing of technology for the processing of liquid radioactive waste from nuclear power plants]. Radiochemistry, vol. 53, no. 5, pp. 470–473. (in Rus.)

5. Andronov O. B. (2015). [On the creation of a modern system for handling liquid radioactive waste at nuclear power plants in Ukraine. Formulation of the problem]. Problems of Nuclear Power Plants Safety and of Chornobyl, vol. 24, pp. 32–41. (in Rus.)

6. Shabalin B. G., Lavrinenko O. M. (2020). Destruction of organic matter from radioactively contaminated water of nuclear power plants equipped with VVER (analytical review). Nuclear Power and the Environment, vol. 18, no. 3, pp. 66–89. (in Ukr.)

7. Tobilko V. Yu., Kornilovich B. K. (2015). [Synthesis and sorption properties of composite materials based on nanosized FeO]. East-­European Journal for Enterprise Technologies, vol. 76, no. 4/5, pp. 22–27. (in Ukr.)

8. Nikitina N. V., Komov D. N., Kazarinov I. A. (2016). [Physical and chemical properties of sorbents based on bentonite clays modified with iron (III) and aluminum polyhydroxocations by the “coprecipitation” method]. Sorption and Chromatographic Processes, no. 2, pp. 191–199. (in Rus.)

9. Nikiforov A. S., Kulichenko V. V., Zhikharev M. I. (1985). Obezvrezhivaniye zhidkikh radioaktivnykh otkhodov [Neutralization of liquid radioactive waste]. Moscow: Energoatomizdat, 184 p. (in Rus.)

10. Shabalin B., Yaroshenko K., Buhera S., Mitsiuk N. (2022). Mineralogical-geochemical properties of bentonite clays of the Cherkasy Deposit to increase the environmental safety of radwaste disposal at the Vektor storage complex. Systems, Decision and Control in Energy III. Studies in Systems, Decision and Control, vol. 399, pp. 203–220. doi.org/10.1007/978–3–030–87675–3_12.

11. Shabalin B. G., Lavrinenko O. M., Yaroshenko K. K., Vember V. V., Buhera S. P. (2021). [Characteristics of products of ozonation of imitations of radioactively fermented trap water of NPP]. Proceedings of the XХIІth International Scientific and Development Conference “Ecology. Man. Society”. Kyiv: NTUU “Igor Sikorsky Kyiv Polytechnic Institute”, pp. 272–276. (in Ukr.)

12. Powder diffraction file 2003. Resource: PDF‑2, Database. Available at: https://www.icdd.com/pdf-2.

13. Avramenko V. A., Yegorin A. M., Sokolnitskaya T. A. (2015). [Sorption-reagent systems in the processing of liquid radioactive waste]. Proceedings of the VIII Russian Conference on Radiochemistry “Radiochemistry‑2015”. Zheleznogorsk, pp. 80–81. (in Rus.)

14. Khodykina M. O. (2017). Formuvannia heterostruktur v systemi neorhanichnyi nosiy-­natyvnyi fermentnyi preparat oksyreduktaz [Molding of heterostructures in the system of inorganic wear-native enzyme preparation oxireductase] (PhD thesis). Kyiv, 136 p. (in Ukr.)

15. Arkhypenko D. (ed.) (1993). Problemy opredeleniya real’noy struktury glaukonitov i rodstvennykh tonkodispersnykh fillosilikatov [Problems of determining the real structure of glauconites and related finely dispersed phyllosilicates]. Kyiv-Novosybirsk: VO “Nauka”, 200 p. (in Rus.)

16. Kroukopova H., Stamberg K. (2005). Experimental study and mathematical modeling of Cs (I) and Sr (II) sorption on bentonite as barrier material in deep geological repository. Acta Geodynamica et Geomaterialia, vol. 2, no. 138, pp. 79–86.

17. Tobilko V. Yu. (2016) Rozrobka sorbtsiynykh tekhnolohiy zakhystu vod vid zabrudnennya vazhkymy metalamy ta radionuklidamy [Development of sorption technologies to protect water from pollution by heavy metals and radionuclides] (PhD thesis). Kyiv, 23 p. (in Ukr.)

18. Walling S. A., Wooyong U., Claire L., Neil C. H. (2021). Fenton and Fenton-like wet oxidation for degradation and destruction of organic radioactive wastes. NPJ Materials Degradation, vol. 5, no. 50. doi.org/10.1038/s41529–021–00192–3.

19. Babuponnusami А., Karuppan Muthukumar K. (2014). A review on Fenton and improvements to the Fenton process for wastewater treatment. Journal of Environmental. Chemical Engineering, vol. 2, pp. 557–572.

20. Kuznetsov V. A., Generalova V. A. (2000). [Study of the sorption properties of iron, manganese, titanium, aluminum and silicon hydroxides with respect to 90Sr and 137Cs]. Radiochemistry, vol. 42, no. 2, pp. 154–157. (in Rus.)

21. Valsala T. P. Joseph Annie, Sonar N. L., Sonavane M. S., Shah J. G., Raj Kanwar, Venugopal V. (2010). Separation of strontium from low-level radioactive waste solutions using hydrous manganese dioxide composite materials. Journal of Nuclear Materials, vol. 404, p. 138.

Full Text (PDF)

---