radioactive materials analytical laboratory eichrom technologies inc. user group meeting may 2001...

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


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


Project: Project: Trace Actinides in Nickel MetalTrace Actinides in Nickel Metal

DOE metals reclamation projectLimited funding21 day turnaround



65% Nickel 30% Copper 2% Iron 6.5 M HNO3

To meet project reporting limits only a max. 20-fold dilution allowed



Reduction of Np– 5mL digestate– 2mL 1M hydroxylamine– Heat between 80C to 100C for

1hr



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



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



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


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


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


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


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)



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



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


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


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



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



Established separation schemes are elaborate, time consuming and more prone to yield reduction



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

radioactive materials analytical laboratory eichrom technologies inc. user group meeting may 2001...

Documents

trace actinides

nickel metal65

reporting limitpcigpcingnggth

mlmin flowrinse

mixed oxide fuels

ancient bone fragments

preconditioned tru resin1

distilled waterload