Abstract
Complex oxides of the pyrochlore (space groups Fd3m, [8]A2 [6]B2O7) and garnet (Ia3d, [8]A3 [6]B2 [4]T3O12) structures (“A” = Ca2+, Ln3+/4+, An3+/4+; “B” = (Ti, Sn, Hf, and Zr)4+ in pyrochlore, and Al3+, Ga3+, and Fe3+ in garnet alone; “T” = (Al3+, Ga3+, and Fe3+) are promising matrices for actinide-bearing wastes. In order to identify optimal compositions of these phases, their isomorphic capacity with respect to REE, actinides, and other components of wastes was examined. The long-term behavior of the matrix at a repository was predicted based on data obtained on the behavior of pyrochlores and garnets under ion irradiation and 244Cm decay and on the determined leaching rates of REE from the matrices because of their interaction with aqueous solutions, including that after amorphization. In order to propose efficient synthesis techniques, samples prepared with the use of various methods were studied. The possibility of incorporating long-lived decay products of 99Tc into the crystalline matrices was analyzed.
Similar content being viewed by others
References
Waste Forms for the Future, Ed. by W. Lutze and R. Ewing (Elsevier, Amsterdam, 1988).
N. P. Laverov, V. I. Velichkin, B. I. Omel’yanenko, et al., Isolation of Spent Nuclear Materials: Geological-Geochemical Principles (IGEM RAN, Moscow, 2008) [in Russian].
A. V. Demine, N. V. Krylova, P. P. Poluektov, et al., “High Level Liquid Waste Solidification Using a “Cold” Crucible Induction Melter,” in Proceedings of Materials Research Society Symposium, Warrendale, US, 2001 (MRS, Warrendale, 2001), Vol. 663, pp. 27–33.
M. I. Solonin, “Treatment Problems of Spent Nuclear Fuel and the Selection of a Locality for Its Storage,” in Proceedings of Seminar on the International Storage of Irradiated Nuclear Fuel, Moscow, Russia, 2003 (Avangard, Moscow, 2005), pp. 33–44 [in Russian].
S. Mtingva, “Possibilities of Transformation of Radioactive Elements,” in Proceedings of Seminar on the International Storage of Irradiated Nuclear Fuel, Moscow, Russia, 2003 (Avangard, Moscow, 2005), pp. 45–72 [in Russian].
B. F. Myasoedov, “Chemical Treatment of High-Level Wastes for the Purpose of Disposal,” in Proceedings of Seminar on the International Storage of Irradiated Nuclear Fuel, Moscow, Russia, 2003 (Avangard, Moscow, 2005), pp. 248–258 [in Russian].
A. A. Kopyrin, A. I. Karelin, and V. A. Karelin, Technology of Production and Radiochemical Recycling of Nuclear Fuel (ZAO “Izd-vo Atomenergoizdat”, Moscow, 2006) [in Russian].
E. B. Anderson, B. E. Burakov, and V. G. Vasiliev, “The Technology of HLW Management in the Project of the Russian Nuclear Fuel Reprocessing Plant,” in Proceedings of International Meeting Nuclear and Hazardous Waste Management, 1994 (Amer. Nucl. Soc. La Grange Park, 1994), Vol. 3, pp. 1969–1975.
A. I. Orlova, V. A. Orlova, M. P. Orlova, et al., “The Crystal-Chemical Principle in Designing Mineral-Like Phosphate Ceramics for Immobilization of Radioactive Waste,” Radiokhimiya 48(4), 297–304 (2006) [Radiochemistry 48, 330–339 (2006)].
G. F. Vandergrift, M. C. Regalbuto, and B. S. Aase, “Lab-Scale Demonstration of the UREX-Process,” in Proceedings of Waste Management Conference, Tucson, US, 2004 (Tuscon, 2004), paper 423.
R. C. Ewing, “The Design and Evaluation of Nuclear Waste Forms: Clues from Mineralogy,” Can. Mineral. 39, 697–715 (2001).
G. R. Lumpkin, “Alpha-Decay Damage and Aqueous Durability of Actinide Host Phases in Natural Systems,” J. Nucl. Mater., No. 289, 136–166 (2001).
R. C. Ewing, W. J. Weber, and J. Lian, “Nuclear Waste Disposal—Pyrochlore (A2B2O7): Nuclear Waste Form for the Immobilization of Plutonium and “Minor” Actinides,” J. Appl. Phys. 95(11), 5949–5971 (2004).
B. I. Omel’yanenko, T. S. Livshits, S. V. Yudintseva, and B. S. Nikonov, “Natural and Artificial Minerals as Matrices for Immobilization of Actinides,” Geol. Rudn. Mestorozhd. 49(3), 173–193 (2007) [Geol. Ore Dep. 49, 173–193].
S. Geller, “Crystal Chemistry of the Garnets,” Zeits. für Kristallogr. 125, 1–47 (1967).
J. Ito and C. Frondel, “Synthesis of Zirconium and Titanium Garnets,” Am. Mineral. 52(5–6), 773–781 (1967).
M. A. Subramanian, G. Aravamudan, and G. V. Subba Rao, “Oxide Pyrochlores—A Review,” Progr. Sol. State Chem. 15, 55–143 (1983).
B. S. Chakoumakos and R. C. Ewing, “Crystal Chemical Constraints on the Formation of Actinide Pyrochlores,” in Proceedings of Material Research Society Symposium, Pittsburgh, US, 1985 (MRS, Pittsburgh, 1985), Vol. 44, 641–646.
C. De Vito, F. Pezzotta, V. Ferrini, and C. Aurisicchio, “Nb-Ti-Ta Oxides in the Gem-Mineralized and ‘Hybrid’ Anjanabonoina Granitic Pegmatite, Central Madagascar: A Record of Magmatic and Postmagmatic Events,” Can. Mineral. 44(Pt. 1), 87–103 (2006).
S. V. Yudintsev, “A Structural-Chemical Approach to Selecting Crystalline Matrices for Actinide Immobilization,” Geol. Rudn. Mestorozhd. 45(2), 172–187 (2003) [Geol. Ore Dep. 45, 151–165 (2003)].
S. V. Yudintsev, S. V. Stefanovsky, and R. C. Ewing, “Actinide Host Phases as Radioactive Waste Forms,” in Structural Chemistry of Inorganic Actinide Compounds, Ed. by S. Krivovichev, P. Burns, and I. Tananaev (Elsevier, Amsterdam, 2007), pp. 453–490.
N. P. Laverov, S. V. Yudintsev, S. V. Stefanovskii, and Y. N. Jang, “New Actinide Matrix with Pyrochlore Structure,” Dokl. Ross. Akad. Nauk 381(3), 399–402 (2001) [Dokl. Earth Sci. 381, 1053–1056 (2001)].
T. S. Livshits and S. V. Yudintsev, “Natural and Synthetic Minerals—Matrices (Forms) for Actinide Waste Immobilization,” in Minerals As Advanced Materials I, Ed. by I. S. Krivovichev (Springer, Berlin, 2008), pp. 193–207.
H. Jaffe, “The Role of Yttrium and Other Minor Elements in the Garnet Group,” Am. Mineral. 36(12), 133–155 (1951).
E. Schingaro, F. Scordari, F. Capitanio, et al., “Crystal Chemistry of Kimzeyite from Anguillara, Mts. Sabatini, Italy,” Eur. J. Mineral. 13, 749–759 (2001).
R. C. Wang, F. Fontain, and X. M. Chen, “Accessory Minerals in the Xihuashan Y-Enriched Granitic Complex, Southern China: a Record of Magmatic and Hydrothermal Stages of Evolution,” Can. Mineral. 41, 727–748 (2003).
I. O. Galuskina, V. M. Gazeev, E. V. Galuskin, et al., “First Find of Uranium Garnet in Nature (Preliminary Report),” in Proceedings of 2nd International Symposium on Uranium: Resources and Production (VIMS, Moscow, 2008), p. 31 [in Russian].
R. C. Ewing, W. J. Weber, and F. W. Clinard, “Radiation Effects in Nuclear Waste Forms for High-Level Radioactive Waste,” Progr. Nucl. Energy 29(2), 63–127 (1995).
G. R. Lumpkin, “Ceramic Waste Forms for Actinides,” Elements 2(6), 365–372 (2006).
W. J. Weber and R. C. Ewing, “Radiation Effects in Crystalline Oxide Host Phases for the Immobilization of Actinides,” in Proceedings of Materials Research Symposium, Warrendale, US, 2002 (Warrendale, 2002), Vol. 713, 443–454 (2002).
N. P. Laverov, S. V. Yudintsev, T. S. Yudintseva, et al., “Effect of Radiation on Properties of Confinement Matrices for Immobilization of Actinide-Bearing Wastes,” Geol. Rudn. Mestorozhd. 45(6), 483–513 (2003) [Geol. Ore Dep. 45, 423–451 (2003)].
J. Lian, S. V. Yudintsev, S. V. Stefanovsky, et al., “Ion Beam Irradiation of U-, Thand Ce-Doped Pyrochlores,” J. Alloys Compd., Nos. 444–445, 429–433 (2007).
S. X. Wang, B. D. Begg, L. M. Wang, et al., “Radiation Stability of Gadolinium Zirconate: A Waste Form for Plutonium Disposition,” J. Mater. Res. 14(12), 4470–4473 (1999).
J. Lian, R. C. Ewing, L. M. Wang, and K. B. Helean, “IonBeam Irradiation of Gd2Sn2O7 and Gd2Hf2O7 Pyrochlore: Bond-Type Effect,” J. Mater. Res. 19, 1575–1580 (2004).
R. C. Ewing, “The Nuclear Fuel Cycle versus the Carbon Cycle,” Can. Mineral. 43, 2099–2116 (2005).
S. V. Yudintsev, A. N. Lukinykh, S. V. Tomilin, et al., “Alpha-Decay Induced Amorphization in Cm-Doped Gd2TiZrO7,” J. Nucl. Mater. 385(1), 200–203 (2009).
S. Utsunomiya, S. V. Yudintsev, and R. C. Ewing, “Radiation Effects in Ferrate Garnet,” J. Nucl. Mater. 336(2–3), 251–260 (2005).
S. V. Stefanovsky, S. V. Yudintsev, R. Gieré, and G. R. Lumpkin, “Nuclear Waste Forms,” in Energy, Waste, and the Environment: A Geochemical Perspective, Ed. by R. Gieré and P. Stille, Geol. Soc. Sp. Publ. London 236, 37–63 (2004).
S. Yudintsev, A. Osherova, A. Dubinin, et al., “Corrosion Study of Actinide Waste Forms with Garnet-Type Structure,” in Proceedings of Materials Research Society Symposium, Warrendale, US, 2004 (MRS, Warrendale, 2004), Vol. 824, 287–292 (2004).
S. V. Stefanovskii, S. V. Yudintsev, and B. S. Nikonov, “Effect of Mechanical Activation on Parameters of Synthesis and Characteristics of Ceramics of Zirconate Pyrochlore,” Fiz. Khim. Obrab. Mater., No. 2, 68–77 (2004).
T. S. Livshits, “Stability of Artificial Ferrite Garnets with Actinides and Lanthanoids in Water Solutions,” Geol. Rudn. Mestorozhd. 49(6), 535–547 (2008) [Geol. Ore Dep. 49, 470–481 (2008)].
Determination of the Chemical Stability of Solidified High-Level Wastes by Long Leaching Technique. GOST R 52126-2003 (Izd-vo standartov, Moscow, 2003) [in Russian].
N. P. Laverov, S. V. Yudintsev, S. V. Stefanovskii, et al., “Phase Formation during the Synthesis of Actinide Matrices,” Dokl. Akad. Nauk 383(1), 95–98 (2002) [Dokl. Earth Sci. 383, 190–193 (2002)].
T. S. Yudintseva, “Study of Synthetic Ferrite Garnets in Context with the Problem of Immobilization of Actinide Wastes,” Geol. Rudn. Mestorozhd. 47(5), 444–450 (2005) [Geol. Ore Dep. 47, 403–409 (2005)]
E. M. Glagovskii, A. V. Kuprin, S. V. Yudintsev, et al., “Peculiarities of Natural Actinide Matrices Obtained by Self-Propagating High-Temperature Synthesis,” Vopr. Radiats. Bezop., No. 2, 21–28 (2002).
S. V. Yudintsev, B. S. Nikonov, E. E. Konovalov, et al., “Study of Matrices Obtained by Self-Propagating HighTemperature Synthesis for Immobilization of HLW,” Fiz. Khim. Obrab. Mater., No. 2, 86–94 (2007).
V. F. Peretrukhin, F. Muazi, A. G. Maslennikov, et al., “Physicochemical Behavior of Uranium and Technetium on Some New Stages of Nuclear fuel Cycle,” Ros. Khim. Zhurnal 51(6), 12–24 (2007).
K. P. Hart, E. R. Vance, R. A. Day, et al., “Immobilization of Separated Tc and Cs/Sr in Synroc,” in Proceedings of Materials Research Society Symposium, Pittsburgh, US, 1996 (MRS, Pittsburgh, 1996), Vol. 41, 281–288 (1996).
E. R. Vance, K. P. Hart, M. L. Carter, et al., “Further Studies of Synroc Immobilization of HLW Sludges and Tc for Hanford Tank Waste Immobilization,” Mater. Res. Soc. Symp. 506, 289–293 (1998).
Exter den M.J., Neumann S., Tomasberger T. “Immobilization and Behavior of Technetium in a Magnesium Titanate Matrix for Final Disposal,” in Proceedings of Materials Research Society Symposium, Warrendale, US, 2006 (MRS, Warrendale, 2006), Vol. 932, pp. 567–574.
E. M. Glagovskii, S. V. Yudintsev, A. V. Kuprin, et al., “Crystalline Host Phases for Actinides, Obtained by Self-Propagating High-Temperature Synthesis,” Radiokhimiya 43(6), 557–562 (2001) [Radiochemistry 43, 632–638 (2001)].
T. V. Barinova, I. P. Borovinskaya, V. I. Ratnikov, and T. I. Ignat’eva, “Self-Propagating High-Temperature Synthesis for Immobilization of High-Level Waste in Mineral-Like Ceramics: 1. Synthesis and Study of Titanate Ceramics Based on Perovskite and Zirconolite,” Radiokhimiya 50(3), 274–278 (2008) [Radiochemistry 50, 321–323 (2008)].
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © N.P. Laverov, S.V. Yudintsev, T.S. Livshits, S.V. Stefanovsky, A.N. Lukinykh, R.C. Ewing, 2010, published in Geokhimiya, 2010, Vol. 48, No. 1, pp. 3–16.
Rights and permissions
About this article
Cite this article
Laverov, N.P., Yudintsev, S.V., Livshits, T.S. et al. Synthetic minerals with the pyrochlore and garnet structures for immobilization of actinide-containing wastes. Geochem. Int. 48, 1–14 (2010). https://doi.org/10.1134/S0016702910010015
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0016702910010015