O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 1 Using Eichrom Resins to Simplify the Analyses for Gallium Content and Atom Percent Fission of Irradiated MOX Fuels J. M. Giaquinto D. L. Denton Oak Ridge National Laboratory* Chemical Sciences Division Oak Ridge, Tennessee *Oak Ridge National Laboratory is managed by UT-Battelle, LLC, for the U.S. Department of Energy under Contract DE-AC05-00OR22725.

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 2 Presentation Overview Fissile Materials Disposition Program Mixed Oxide Fuel Assembly Separations for Gallium Analysis Separations for Atom Percent Fission Some Burnup Results vs. Predicted Conclusions

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 3 Fissile Materials Disposition Program (FMDP) International effort to reduce highly enriched uranium and weapons-grade plutonium stockpiles. Sep93: Pres. Clinton commits U.S. to eliminate or reduce stockpiles. Dec96: DOE announces preferred approach for disposal of plutonium will be LWRs. Dec01: Pres. Bush endorses moving forward with a surplus weapons plutonium program based on using LWRs. ORNL is the lead laboratory for the reactor based initiative. Mar05: NRC issues licensing amendments for Duke Power to allow the receipt and use of four MOX fuel lead assemblies.

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 4 Why Gallium? Commercial light water reactors use a zirconium alloy for the fuel clad material. Gallium will attack zirconium metal. Weapons-grade plutonium contains gallium. Will gallium migrate from the fuel into the clad material and cause degradation?

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 5 Why Atom Percent Fission Analysis? Precise documentation of irradiation period for the various tests (PIEs, gallium, fission gas release, etc.) Validation of INEL computer codes (Gray Chang)

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 6 MOX Pellets Fabricated at LANL ~95% uranium (~99% U-238) ~5% plutonium (~94% Pu-239)

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 7 Test Assembly Stainless Steel outer cladding Zircaloy inner cladding 15 MOX pellets Irradiated in the Advanced Test Reactor (INEL)

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 8 Un-irradiated MOX Solution Scan

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 9 Un-irradiated Clad Solution Scan

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 10 MOX Fuel Fission Products Scan

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 11

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 12 TRU Resin Separation -Conditioned with 4 M HNO 3. -Loaded matrix exchanged aliquot onto column. - Rinsed with 4 M HNO 3. - Rinse collected with earlier eluant.

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O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 14 Sr/TRU Resin Separation Condition with 6M HNO 3 (20mL) Load matrix exchanged aliquots onto columns Rinse with 6M HNO 3 (7-8mL)

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 15 Irradiated MOX Post Sr/TRU Separation

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 16 Irradiated Clad Post Sr/TRU Separation

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 17 Poor Ba and FP Removal in Clads ~6,000 ug Zr in load solution HF complexed with boric acid and matrix exchange into nitric acid Manageable interferences High Sn in solution has caused flow problems with some samples

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 18 ASTM E Overview U, Pu, and the Nd fission products are chemically separated and determined by IDMS Atom fractions are calculated for the dominate contributors and fission product 148 Nd The atom fraction of fuel consumed is equal to the atom fraction of 148 Nd/ 148 Nd effective yield Percent burnup is calculated by dividing the atom fraction of fuel consumed by the unirradiated sum of the dominate fissionable isotopes

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 19 High Mass Fission Products Nd CsBaLaCePrCe Sm Eu Sm Eu Sm Natural Nd check mass Spike mass Burnup mass

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 20 ASTM E Nd Separations

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 21 Eichrom Technologies Ln Resin di(2-ethylhexyl) orthophosphoric acid (HDEHP) Hydrophobic support Resin capacity: 2-4 mg Nd/mL Ln resin

O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 22 Ln Resin Simplified Separation 5 mL to 6 mL bed volume Resin conditioned with 0.18 M HCl Sample matrix adjusted to 0.18 M HCl Sample loaded onto column and rinsed through with 0.18 M HCl. Eluant collected in 5 mL fractions. Nd fractions combined for MS analysis

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O AK R IDGE N ATIONAL L ABORATORY U. S. D EPARTMENT OF E NERGY 25 Conclusions Combining Eichrom Sr and TRU Resins provide for a simple and effective solution for Ga analysis by ICPMS Eichrom Ln resin provides for an effective baseline separation of the high mass fission products (REEs) Data supports FMDP goals for reducing Pu stockpiles by using MOX fuels in commercial LWRs. Security and waste issues still remain however.