Actinides immobilization

During the past ten years, there has been considerable research devoted to the development of crystalline waste forms for actinide immobilization [7,8,24,27, 28,39,40,67,68,41-43,69]. Many of the phases are based on studies of minerals that contain Th and U, such as pyrochlore [16-18], zirconolite [70,71], zircon [1,72], monazite [73], britholite [74]. Based on their degrees of alteration, most of the minerals are considered to have an acceptable chemical durability. In addition, closely related mineral structures, such as murataite and garnet, which do not contain U or Th have been synthesized with actinides [29,75,76]. Multiphase ceramics. Ceramic matrices were initially designed for the immobilization of non-partitioned HLW from SNF reprocessing and considered... 

Simple thermodynamic calculations based on literature data (5-12) support the choice of phosphates as the optimum mineral phases for actinide immobilization. The calculations considered every relevant species reported (5-72) that contained protons, hydroxide, or the ligand in question for each metal ion. Where necessary, equilibrium constants were corrected to 0.1 M ionic strength using the Davies equation. As an example, the calculated solubility of europium, thorium, and uranium in various media at p[H] 7.0 (p[H] = - log of the hydrogen ion concentration), 0.001 M total ligand concentration, 0.1 M ionic strength, and 25 °C are shown in Table I. Within the constraints of the calculation, the solubility of thorium is limited by Th(OH)4, but the lowest europium and uranyl solubilities are observed for phosphates. 

While each of the above technologies offers certain unique advantages, those common to ceramic immobilization include a relative ease in fabrication, a high capacity for actinides or heavy metals compared to other technologies, the capacity for flexibility of feedstock, the ability to add neutron absorber materials for nuclear waste applications, and the ability to control the properties of the final waste form. 

Ewing, R. C., Weber, W. J. Lian, J. (2004) Pyrochlore (A2B2O7) A nuclear waste form for the immobilization of plutonium and minor actinides. Journal of Applied Physics, 95, 5949-5971. 

Bibler, N. E., Ramsey, W. G., Meaker, T. F. Pareizs, J. M. 1996. Durabilities and microstructures of radioactive glasses for immobilization of excess actinides at the Savannah River site. Materials Research Society Symposium Proceedings, 412, 65 - 72. 

Stefanovsky, S. V., Yudintsev, S. V., Nikonov, B. S., Omelianenko, B. I. Ptashkin, A. G. 1999. Murataite-based ceramics for actinide waste immobilization. Materials Research Society Symposium Proceedings, 556, 121-128. 

Cherniavskaya, N. E. 2000a. Phase compositions and elements partitioning in two-phase hosts for immobilization of rare earth - actinide high level waste fraction. Materials Research Society Symposium Proceedings, 608, 455-460. 

Weber, W. J. Ewing, R. C. 2002. Radiation effects in crystalline oxide host phases for the immobilization of actinides. Materials Research Society Symposium Proceedings, 713, 443-454. 

Yudintsev, S. V., Stefanovsky, S. V. Ewing, R. C. 1999. Structural and compositional relationships in titanate-composed ceramics for actinide-bearing waste immobilization. In Proceedings of the 7th International Conference on Radioactive Waste Management and Environmental Remediation ICEM 99. Nagoya, Japan, CD-ROM. 

Pu(IV), which forms highly charged polymers, strongly sorbs to soils and sediments. Other actinide III and IV oxidation states also bind by ion exchange to clays. The uptake of these species by solids is in the same sequence as the order of hydrolysis Pu > Am(III) > U(VI) > Np(V). The uptake of these actinides by plants appears to be in the reverse order of hydrolysis Np(V) > U(VI) > Am(III) > Pu(IV), with plants showing little ability to assimilate the immobile hydrolyzed species. The further concentration of these species in the food chain with subsequent deposit in humans appears to be minor. Of the 4 tons of plutonium released to the environment in atmospheric testing of nuclear weapons, the total amount fixed in the world population is less than 1 g [of this amount, most (99.9%) was inhaled rather than ingested]. 

The largest number of automated extraction-chromatographic separations for actinides have used TRU-Resin, and many of these have coupled the column to ICP-MS as an on-line separation (see Table 9.3). TRU-Resin is impregnated with the neutral bifunctional organophosphorus complexant, octyl(phenyl)-A,A-diisobu-tylcarbamoylmethylphosphine oxide (CMPO) in tri-n-butyl phosphate (TBP).26 127 128 The organic stationary phase in this resin binds trivalent, tetravalent, and hexavalent actinide nitrato complexes from nitric acid solutions (see Figure 9.11). The extraction equilibria for representative species are shown in Equations 9.3-9.5, where the bar above a species indicates that it is immobilized on the resin.4... 

Fly ash increases the density, decreases the permeability, and increases the leaching resistance of Ordinary Portland Cement (OPC). It is a truism that The leach resistance of solidified cement-waste systems can be improved by any process which accelerates curing, limits porosity, or chemically bonds fission product or actinide elements. (Jantzen et al., 1984). Supercritical C02 treatment of a modified Portland cement is expected to further increase the density over the untreated material, so that a reduced porosity and improved leachability should result. In addition, the high silica content of fly ash, with its well-known sorbent properties toward actinides and certain other radionuclides, enhances the immobilization characteristics. 

As mentioned in Section 17.3.1, retention of quadrivalent actinide oxides within the phosphate matrix is not a major issue because these oxides are insoluble in water, and all that is needed is their microencapsulation by the phosphate components of the matrix. This was demonstrated in a number of studies on UO2 and PUO2 and their surrogate Ce02. If the actinides are found in a trace amount in the waste, their chemical form is not so important because the phosphate matrix immobilizes them very efiectively. For example, the wastewater in the case study given in Section 16.3.2.2 contained 32 pCi/ml of and 0.6 pCi/ml of The ANS 16.1 tests conducted on the waste forms with 18.6pCi/g loading of combined U in the waste form showed that the leaching index was 14.52. XCLP tests also showed that levels in the leachate were below the detection limit of 0.2 pCi/ml. This implies that microencapsulation of trace-level U is very efiective in the Ceramicrete matrix. 

Gauglitz R., Holterdorf M., Franke W., and Marx G. (1992) Immobilization of actinides by hydroxylapatite. In Scientific Basis for Nuclear Waste, Management XV, Materials Research Society Symposium Proceedings (ed. C. G. Sombret). Materials Research Society, Pittsburgh, PA, vol. 257, pp. 567-573. 

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