Radioactive Materials Analytical Laboratory
Eichrom Technologies Inc. User Eichrom Technologies Inc. User Group Meeting May 2001Group Meeting May 2001
J.M. Giaquinto, L.D. Bible, D.C. Glasgow, J.M. Keller
Chemical and Analytical Sciences Division
Oak Ridge National Laboratory
Radioactive Materials Analytical Laboratory
Projects To Be DiscussedProjects 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
Radioactive Materials Analytical Laboratory
Project: Project: Trace Actinides in Nickel MetalTrace Actinides in Nickel Metal
DOE metals reclamation projectLimited funding21 day turnaround
Radioactive Materials Analytical Laboratory
Project: Project: Trace Actinides in Nickel MetalTrace Actinides in Nickel Metal
65% Nickel 30% Copper 2% Iron 6.5 M HNO3
To meet project reporting limits only a max. 20-fold dilution allowed
Radioactive Materials Analytical Laboratory
Project: Project: Trace Actinides in Nickel MetalTrace Actinides in Nickel Metal
Reduction of Np– 5mL digestate– 2mL 1M hydroxylamine– Heat between 80C to 100C for
1hr
Radioactive Materials Analytical Laboratory
Project: Project: Trace Actinides in Nickel MetalTrace 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 HNO3
Radioactive Materials Analytical Laboratory
Project: Project: Trace Actinides in Nickel MetalTrace Actinides in Nickel Metal
Sample elution– Elute with 10 mL of 0.1 M
oxalate in 0.005 M HNO3
• 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 HNO3
Ready for ICPMS analysis
Radioactive Materials Analytical Laboratory
Project: Project: Trace Actinides in Nickel MetalTrace Actinides in Nickel Metal
20%30%40%50%60%70%80%90%
100%110%120%130%
Percent Recovery
Th-232 83% 73% 99% 90% 120%
U-233 76% 74% 49% 97% 93% 91% 96%
Np237 93% 92% 36% 75% 93% 90% 97%
Pu-242 101% 99% 46% 81% 100% 99% 102%
1 2 33 re-prep
4 5 6
MatrixSpike Recoveries
Radioactive Materials Analytical Laboratory
Project: Project: Trace Level Gallium Analysis in MOX Trace Level Gallium Analysis in MOX Fuels (Irradiated and Un-Irradiated)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
Radioactive Materials Analytical Laboratory
Radioactive Materials Analytical Laboratory
Radioactive Materials Analytical Laboratory
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
Radioactive Materials Analytical Laboratory
Radioactive Materials Analytical Laboratory
Project: Project: Trace Level Gallium Analysis in MOX Trace Level Gallium Analysis in MOX Fuels (Irradiated and Un-Irradiated)Fuels (Irradiated and Un-Irradiated)
MatrixSpike Recoveries
20%
30%
40%
50%
60%
70%
80%
90%
100%
110%
120%
130%
Percent Recovery
Ga 96% 95% 94% 92% 92% 91% 107%
1 2 3 4 5 6 7
Radioactive Materials Analytical Laboratory
Project: Project: Baseline Separation of High Mass Fission Baseline Separation of High Mass Fission Products (REEs) For Burn-up CalculationsProducts (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)
Radioactive Materials Analytical Laboratory
Project: Project: Baseline Separation of High Mass Fission Baseline Separation of High Mass Fission Products (REEs) For Burn-up CalculationsProducts (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
Radioactive Materials Analytical Laboratory
Radioactive Materials Analytical Laboratory
Project: Project: Baseline Separation of High Mass Fission Baseline Separation of High Mass Fission Products (REEs) For Burn-up CalculationsProducts (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
Radioactive Materials Analytical Laboratory
Baseline separation of Ce, Nd, and Sm Using Eichrom LN Resin
0
2000
4000
6000
8000
10000
12000
14000
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Fraction
Inte
rgra
ted
Cou
nts
Ce 140
Ce142
Nd143
Ce/Nd144
Nd145
Nd146
Nd148
Nd150
Sm152
Radioactive Materials Analytical Laboratory
Project: Project: Trace Level Iridium Analysis In Ancient Trace Level Iridium Analysis In Ancient Bone Fragments By NAABone 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
Radioactive Materials Analytical Laboratory
Project: Project: Trace Level Iridium Analysis In Ancient Trace Level Iridium Analysis In Ancient Bone Fragments By NAABone Fragments By NAA
Neutron Activation Analysis for Iridium
191Ir
193Ir (n,gamma)
(n,gamma) 192Ir
194Ir
gamma
gamma
T 1/2=74 days
T 1/2=19 hrs
316 KeV
328 KeV
Radioactive Materials Analytical Laboratory
Project: Project: Trace Level Iridium Analysis In Ancient Trace Level Iridium Analysis In Ancient Bone Fragments By NAABone Fragments By NAA
Established separation schemes are elaborate, time consuming and more prone to yield reduction
Radioactive Materials Analytical Laboratory
Project: Project: Trace Level Iridium Analysis In Ancient Trace Level Iridium Analysis In Ancient Bone Fragments By NAABone Fragments By NAA
TEVA Separation:– Load sample digestion (8 M HNO3/6 M
HCl) onto column treated with 2 M HNO3
– Pass through with vacuum
– Wash with 2.5 mL of 2 M HNO3
– Dry and seal column for neutron activation