2002 Denver Annual Meeting (October 27-30, 2002)

Paper No. 9
Presentation Time: 1:30 PM-5:30 PM


PIERCE, E.M.1, SERNE, R.J.2, ICENHOWER, J.P.2 and MARTIN, W.J.2, (1)Graduate School, Tulane Univ, New Orleans, LA 70118, (2)Pacific Northwest National Lab, 902 Battelle Boulevard, PO Box 999, MS K6-81, Richland WA, WA 99352, Eric.Pierce@pnl.gov

To evaluate the possibility of utilizing REDOX permeable reactive barriers for the remediation of uranium contamination, knowledge of the fundamental reaction kinetics associated with the dissolution of reduced uranium (IV) dioxide is necessary.  Four decades of existing UO2+x (cr) (0 < x < 0.33) dissolution studies, focusing on spent nuclear fuel disposal, have generated numerous inconsistencies and unanswered questions.  A cardinal gap in our understanding is the relationship between UO2+x (cr) dissolution rate and bicarbonate activity.  To resolve the inconsistencies we have conducted several UO2 dissolution experiments under oxic conditions in the presence of [HCO3-] = 0.1 M; at pH = 8.0; flow rates (q) = 6, 24, 48, and 120 mL d-1; geometric surface area (S) = 10-3 m2 g-1, and temperatures (T) = 30 and 60oC using a single pass flow-through apparatus.

The UO2 was characterized using a suite of analytical and chemical techniques (XRD, XAS, SEM, and chemical digestion).  Analyses confirm that the UO2 specimen is ~ 99.9% pure with trace amounts of Co2O3, CuO, NiO, and SrO, and dominated by the UIV oxidation state with a UIV-O oxygen bond length of approximately 2.2 Å in the first shell.  SEM images of powdered specimens show that the non-fractured particles are spherical and appear to be relatively porous.

Experiments with high flow rates (120-mL d-1) achieve steady-state U release rates after the 4th day, which corresponds to approximately 8 reactor volumes.  The elemental release rate of U from the UO2 specimen increases by an order of magnitude with each 30-degree increase in temperature.  Measured log10 rates (in mol m-2 s-1) at 30ºC are -7.45±0.07 and 60ºC are -6.53±0.06.   Additional experiments over a range of flow rates indicate that the dissolution rate is not only dependent on T, but also the ratio of flow to sample surface area (i.e., q/S). In all cases, rates become constant at high values of q/S, indicating the influence of chemical affinity on the dissolution kinetics.

U dissolution rates obtained in this study are 1 to 2 orders of magnitude larger than previously reported rates and may reflect their dependence on the ratio of q/S or on bicarbonate activity.  Our results highlight the importance of understanding the role between bicarbonate activity, solution saturation state, and dissolution kinetics.