Effect of Radionuclides on the Corrosion of Low Carbon Steel in High Level Nuclear Waste Storage Conditions

"High-level radioactive wastes are stored in large underground storage tanks made of low-carbon steel. The wastes consist of concentrated solutions of sodium nitrate (NaNO3) and sodium hydroxide (NaOH), and the radionuclides 137Cs, 99Tc, and 90Sr. The corroding steel microenvironment may produce localized reducing or oxidizing conditions that affect the solubilities of the species such as Tc(VII) and Tc(IV), which in turn modifies the kinetics of corrosion of the storage tank. To understand the influence of technetate ions on the corrosion of steel, electrochemical polarization studies of A 537 steel samples were carried out in 1 M NaNO3 + 0 .05 M S r(NO3)2 + 0.1 M NaOH with and without addition of HReO4 at different temperatures (24 – 85 °C). The concentration of HReO4 was varied from 0.014 – 0.04 M.INTRODUCTIONAqueous processing of spent nuclear materials generates a large amount of high-level radioactive wastes. The wastes are primarily salt solutions of sodium hydroxide and sodium nitrate which also contain fission products such as 137Cs, 99Tc, and 90Sr. Among the high level radioactive fission products, Tc-99 is of great importance because of its high concentration, long half-life (2.1 x 105 years), high solubility in geologic waters as technetate, and rapid diffusivity through the geologic systems. The solubility of technetate ions varies depending on the oxidizing conditions prevailing in the storage containers. High level radioactive wastes are stored in single shell or double shell tanks made of low carbon steels such as ASTM type A15, A516-70 and A537. Most of the available literature on corrosion of steel in simulated radio active waste environments pertains to nitrate induced stress corrosion cracking (Subramanian & Mickalonis, 2005). The corroding steel microenvironment may produce localized reducing or oxidizing conditions that affect the solubilities of the species such as Tc(VII) and Tc(IV). Corrosion of steel and formation of Fe(II) and Fe(III) will affect adsorption and reduction of Tc species. The radioactive species can irreversibly be sorbed on the steel surface by oxidation of Fe(II) to more stable Fe(III) and fixed as less soluble Tc(IV)/Fe(III). The solubility of Tc species is also affected by other factors such as dissolved oxygen, local pH, temperature etc. How the corrosion behavior of steel will be affected in the presence of Tc species is not clearly understood.Cartledge (Cartledge, 1960) demonstrated that passivation of iron can be achieved in the presence of oxygen along with suitable inhibitor ions/molecules of the general formula XO4 n-, such as pertechnetate (TcO4 -). The pertechnetate ion is univalent. Since it is derived from a strong acid, no buffering action can be expected from this ion. The redox potential of the reaction (1) is 0.738 VSHE (Pourbaix, 1974)."