j. m. giaquinto d. l. denton oak ridge national laboratory* chemical sciences division

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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY

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 37831-6043

*Oak Ridge National Laboratory is managed by UT-Battelle, LLC, for the U.S. Department of Energy under Contract DE-AC05-00OR22725.

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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

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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.

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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?

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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)

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MOX Pellets

Fabricated at LANL ~95% uranium (~99%

U-238) ~5% plutonium

(~94% Pu-239)

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Test Assembly

Stainless Steel outer cladding

Zircaloy inner cladding

15 MOX pellets Irradiated in the

Advanced Test Reactor (INEL)

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Un-irradiated MOX Solution Scan

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Un-irradiated Clad Solution Scan

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MOX Fuel Fission Products Scan

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TRU Resin Separation-Conditioned with 4 M

HNO3.-Loaded matrix

exchanged aliquot onto column.- Rinsed with 4 M HNO3.- Rinse collected with

earlier eluant.

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Sr/TRU Resin Separation

Condition with 6M HNO3 (20mL)

Load matrix exchanged aliquots onto columns

Rinse with 6M HNO3 (7-8mL)

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Irradiated MOX Post Sr/TRU Separation

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Irradiated Clad Post Sr/TRU Separation

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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

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ASTM E321 96 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 148Nd

The atom fraction of fuel consumed is equal to the atom fraction of 148Nd/148Nd effective yield

Percent burnup is calculated by dividing the atom fraction of fuel consumed by the unirradiated sum of the dominate fissionable isotopes

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High Mass Fission Products

Nd Nd Nd Nd Nd Nd

Cs Ba La Ce Pr Ce Ce Sm Sm Sm Sm Eu Sm Eu Sm

Natural Nd check mass

Spike mass

Burnup mass

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ASTM E321 96 Nd Separations

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Eichrom Technologies Ln Resin

di(2-ethylhexyl) orthophosphoric acid (HDEHP)

Hydrophobic support Resin capacity: 2-4

mg Nd/mL Ln resin

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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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6mL bed volume Ln column 0.180M HCl load and elution (irradiated MOX fuel)

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

Co

un

ts

Ce 140

Ce142

Nd143

Ce/Nd144

Nd145

Nd146

Nd148

Nd150

Sm152

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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.

j. m. giaquinto d. l. denton oak ridge national laboratory* chemical sciences division

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