1. Radioactive Materials Analytical Laboratory Eichrom Technologies Inc. User Group Meeting May 2001 J.M. Giaquinto, L.D. Bible, D.C. Glasgow, J.M. Keller Chemical and Analytical Sciences Division Oak Ridge National Laboratory

2. Radioactive Materials Analytical Laboratory Projects To Be Discussed Trace level actinides analysis in nickel metal Trace level gallium analysis in mixed oxide fuels (irradiated and un-irradiated) Baseline separation of high mass fission products (REEs) for burn-up analysis and calculation Trace level iridium analysis in ancient bone fragments by NAA

3. Radioactive Materials Analytical Laboratory Project: Trace Actinides in Nickel Metal DOE metals reclamation project Limited funding 21 day turnaround

4. Radioactive Materials Analytical Laboratory Project: Trace Actinides in Nickel Metal 65% Nickel 30% Copper 2% Iron 6.5 M HNO 3 To meet project reporting limits only a max. 20-fold dilution allowed

5. Radioactive Materials Analytical Laboratory Project: Trace Actinides in Nickel Metal Reduction of Np –5mL digestate –2mL 1M hydroxylamine –Heat between 80C to 100C for 1hr

6. Radioactive Materials Analytical Laboratory Project: Trace Actinides in Nickel Metal Sample loading –Let solution cool –Build to ~7 mL with distilled water –Load onto pre- conditioned TRU Resin 1 to 2 mL/min flow –Rinse with 5 mL of 4 M HNO 3

7. Radioactive Materials Analytical Laboratory Project: Trace Actinides in Nickel Metal Sample elution –Elute with 10 mL of 0.1 M oxalate in 0.005 M HNO 3 1 to 2 mL/min flow Matrix adjustment –Heat eluant at 100C to 150C until volume reduced to ~2 mL Destroy oxalate –Cool and collect solution. Build to 5 mL with 0.5 M HNO 3 Ready for ICPMS analysis

8. Radioactive Materials Analytical Laboratory Project: Trace Actinides in Nickel Metal Matrix Spike Recoveries

9. Radioactive Materials Analytical Laboratory Project: Trace Level Gallium Analysis in MOX Fuels (Irradiated and Un-Irradiated) Analysis performed at the request of the Fissile Materials Disposition Program (FMDP) Gallium mixed with the plutonium product Reporting limits in the 10’s of ppb required for the un-irradiated enriched uranium product

10. Radioactive Materials Analytical Laboratory

12. TRU Resin Separation -Sample digestion matrix adjusted to 2.5 M to 4.0 M nitric acid. -5 mL portion passed through column conditioned with 2.5 M nitric acid. Elution collected. - Column rinsed with 5 mL 2.5 M nitric acid. Rinse collected with earlier eluant - Volume adjusted if needed. Ready for ICP-MS analysis

13. Radioactive Materials Analytical Laboratory

14. Project: Trace Level Gallium Analysis in MOX Fuels (Irradiated and Un-Irradiated) Matrix Spike Recoveries

15. Radioactive Materials Analytical Laboratory Project: Baseline Separation of High Mass Fission Products (REEs) For Burn-up Calculations Analysis performed at the request of the Fissile Materials Disposition Program (FMDP) ASTM E 321-96 Standard Test Method for Atom Percent Fission in Uranium and Plutonium Fuel (Nd-148 Method)

16. Radioactive Materials Analytical Laboratory Project: Baseline Separation of High Mass Fission Products (REEs) For Burn-up Calculations Uranium and Plutonium fractions are separated using Anion Exchange Resin Neodymium fraction –ASTM separation Time consuming Multiple reagents –Eichrom Ln Resin Simple separation scheme One reagent (0.18 M HCL) Can re-use column once it is calibrated

17. Radioactive Materials Analytical Laboratory

18. Project: Baseline Separation of High Mass Fission Products (REEs) For Burn-up Calculations Ln Resin 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 and dried for TIMS analysis

19. Radioactive Materials Analytical Laboratory

20. Project: Trace Level Iridium Analysis In Ancient Bone Fragments By NAA Cretaceous-Tertiary (K/T) geological boundary is defined by an excessive deposit of iridium Typically iridium present at ultra- trace (<100ppt) levels in materials of geological interest Separation needed to isolate and concentrate Ir for NAA

21. Radioactive Materials Analytical Laboratory Project: Trace Level Iridium Analysis In Ancient Bone Fragments By NAA Neutron Activation Analysis for Iridium 191 Ir 193 Ir (n,gamma) 192 Ir 194 Ir gamma T 1/2 =74 days T 1/2 =19 hrs 316 KeV 328 KeV

22. Radioactive Materials Analytical Laboratory Project: Trace Level Iridium Analysis In Ancient Bone Fragments By NAA Established separation schemes are elaborate, time consuming and more prone to yield reduction

23. Radioactive Materials Analytical Laboratory Project: Trace Level Iridium Analysis In Ancient Bone Fragments By NAA TEVA Separation: –Load sample digestion (8 M HNO 3 /6 M HCl) onto column treated with 2 M HNO 3 –Pass through with vacuum –Wash with 2.5 mL of 2 M HNO 3 –Dry and seal column for neutron activation