The largest amount of actinides possibly to be released into the environment, however, can be attributed to the geological disposal of spent nuclear fuel. Neptunium is more environmentally mobile than other transuranic elements and thus could escape into the environment. The long-lived neptunium isotope Np-237 (2.14 x 10^6 y) is an actinide of concern in safety assessments of a spent nuclear fuel repositories. It is created by irradiating uranium (U-235 or U-238) in a nuclear reactor and also formed from the decay of americium (Am-241). Radiotoxic Np-237 has been identified as a dominant long-term dose contributor of nuclear waste after one million years. The Np oxidation states under environmental conditions are Np(IV) and Np(V). Under mildly oxic conditions, Np(V) is likely to be the dominant oxidation state. Neptunium is quite soluble, poorly sorbed, and readily mobile under environmental conditions making it highly relevant for research within nuclear safety aspects. Aluminosilicate clay minerals are known to sorb actinides and contribute to actinide immobilization. However, their sorption to these same minerals may also result in colloid-facilitated transport. The bentonite buffer used in the Engineered Barrier System (EBS) consists mainly of montmorillonite and is assumed to be a potential source of colloids. The potential relevance of colloids for radionuclide transport is highly dependent on the stability of colloids in different chemical environments and their interaction with radionuclides. The dimensions of colloids are 1 – 1000 nm and they have strong sorbing properties due to large specific surface area and surface charge. In low salinity groundwater conditions, colloids are mobile unlike rock surfaces. Np(V) sorption behavior on clay minerals has been previously investigated in relatively few studies.
In this study, the interaction of neptunium with the clay mineral montmorillonite and bentonite colloid suspension was investigated under simplified but environmentally relevant conditions. Sorption of Np(V) on corundum, Na-montmorillonite and bentonite colloids was studied by conducting batch experiments. Zeta potential measurements were made to obtain data from the surface potential of montmorillonite. Specific surface area, BET, measurements were conducted for montmorillonite and bentonite to get information of the possible sorption capacities. In situ Attenuated Total Reflection (ATR) FT-IR spectroscopy determinations were made to identify neptunium's surface speciation. Aim of the ATR FT-IR measurements is to identify the dominating surface reactions during the sorption of neptunium on mineral and colloid surfaces and to describe them with suitable surface complex formation models.
Due to the results the neptunium adsorption onto corundum, montmorillonite and bentonite colloids is detectable. The neptunium adsorption increases as the pH of the solution increases. The sorption is relevant in pH 9 - 11. More isotherm studies are needed to examine the possible saturation of the sorption places for neptunium on the montmorillonite. In addition the reversibility, observed in the ATR FT-IR measurements, of the neptunium sorption should be studied also in batch experiments. The bond between neptunium and corundum or montmorillonite, based on zeta potential and ATR FT-IR measurements, seems to be an inner-sphere complex. For bentonite colloids it was not possible to measure ATR FT-IR because the colloids did not sorb enough neptunium to obtain any spectra. Although the ATR FT-IR measurements showed high reversibility for the bond, indicating it is rather weak inner-sphere complex.
