Neptunium Oxide Precipitation Kinetics in Aqueous Systems at Elevated Temperatures, Part I: Colloidal, Temperature, Inert Atmosphere, and Ionic Strength Measurements
We evaluate the proposed NpO 2 + (aq)-NpO 2 (cr) reduction-precipitation system at elevated temperatures to obtain primary information on the effects of temperature, ionic strength, O 2 and CO 2 . Experiments conducted on unfiltered solutions at 10 -4 M NpO 2 + (aq), neutral pH, and 200°C indicated that solution colloids strongly affect precipitation kinetics. Subsequent experiments on filtered solutions at 200, 212, and 225°C showed consistent and distinctive temperature-dependent behavior at reaction times ≤ 800 hours. At longer times, the 200°C experiments showed unexpected dissolution of neptunium solids, but experiments at 212°C and 225°C demonstrated quasi steady-state neptunium concentrations of 3 x 10 -6 M and 6 x 10 -6 M, respectively. Solids from a representative experiment analyzed by X-ray diffraction were consistent with NpO 2 (cr). A 200°C experiment with a NaCl concentration of 0.05 M showed a dramatic increase in the rate of neptunium loss. A 200°C experiment in an argon atmosphere resulted in nearly complete loss of aqueous neptunium. Previously proposed NpO 2 + (aq)-NpO 2 (cr) reduction-precipitation mechanisms in the literature specified a 1:1 ratio of neptunium loss and H + production in solution over time. However, all experiments demonstrated ratios of approximately 0.4 to 0.5. Carbonate equilibria can account for only about 40% of this discrepancy, leaving an unexpected deficit in H + production that suggests that additional chemical processes are occurring.