A Rapid Analysis of Actinides In Urine Samples Using

Eichrom’s Resin Cartridges Anil H.Thakkar

Eichrom Industries, Inc..Darien, IL

Objective

• To perform analysis for Am, Pu and U in urine samples using Eichrom’s new chromatographic configuration of UTEVA and TRU Resin

Current Eichrom Method

•UTEVA and TRU Resin Column

•Industry Standard

•Flow Rate Limitation

Precedent: Actinides in Water• 1 liter water samples• Coprecipitate with calcium phosphate• Dissolve in load solution• Load on UTEVA and TRU columns in

tandem

Tandem Column Arrangement

Discard

T

R

U

U

T

E

V

A Strip

Strip

PuU

Am

Load

Eichrom UTEVA Resin Column Separation

Load: 3M HNO3, 1.0M Al(NO3)3

0.01M HCl

to TRU Resin column

U

Eichrom TRU Resin Column Separation

Load: 3 M HNO3, 1.0M Al(NO3)3

9m HCl & 4M HCl

0.1M ammonium bioxalate

to waste

Am

Pu

Decontamination Factors (DF)

• To determine the ruggedness of the method

• To determine the degree of separation of the analyte from potentially interfering matrix components

Experiment for DF

•Approximately 100 pCi (3.7 Bq) of each actinide was added to a load solution and run through the method.

•DF in uranium, plutonium and americium fractions were calculated.

Equation for Decontamination Factor

DF = Ao

Af

Where; Ao = Original activity of the analyte added

Af = Final activity of analyte in the fraction

Criteria for Acceptance

• For actinides, a DF value of > 1000 is acceptable

• Tracer Recovery: 70%-105%

Decontamination Factors (with column)

Actinide DF in U fraction

DF in Pu fraction

DF in Am fraction

U-232 N/A 3300->5600 900->4000

Pu-242 1200-1400 N/A >2400

Am-243 1400->4300 1600 N/A

Th-228 2800-3300 3400-4000 >3600

Np-237 1100-1200 3500->3900 >3900

New Configuration:Resin Cartridge

• Packed with 2 mL of resin

• Cartridges with Luer lock

• Ease of tandem arrangement for sequential analysis

Eichrom Vacuum Box System

• 24 Hole clear polycarbonate vacuum box• Inexpensive cartridge connection

– Yellow outer tip provides support– White inner tip provides excellent seal

• Vacuum gauge• Plastic rack for twenty four 50 mL C Tubes• Eichrom has limited stock on hand

Decontamination Factors (with Cartridge)

Actinide DF in U fraction

DF in Pu fraction

DF in Am fraction

U-232 N/A 7300 >5800

Pu-239/240 12,000 N/A 7000

Am-241 >6600 20,000 N/A

Th-229 15,000 10,000 >10,000

Np-237 3500 7000 >12,000

Sample Preparation• 1.2 liter aliquots of acidified urine samples

were spiked with Am, Pu and U• Samples were heated to near boiling for 2

hours • A Ca3(PO4)2 precipitation was performed• Decant supernatant, centrifuge and collect

the precipitate• Perform a wet digestion on the precipitate

until white ash

Load Solution for UTEVA and TRU Resin Columns

• Dissolve precipitate in 3M HNO3/1M Al(NO3)3 solution

• Add ferrous sulfamate and ascorbic acid• Load on UTEVA and TRU Resin cartridge

in tandem

Am/Cm, Pu and U AnalysesCalcium phosphate precipitation

Wet ash digestion

Eichrom U/TEVA Resin U

Eichrom TRU Resin Am/Cm, Pu

Preparation for counting

Alpha spectrometry

Flow rate•Sample load: Typically 1 mL/minute

•Rinse solution: 2-3 mL/minute

•Strip solution: 1 mL/minute

•Achievable with vacuum pump

Recoveries for Direct Spikes

Actinide Column Cartridge

Am 88% 75+12%(n=4)

U 100% 89+6% (n=4)

Pu 83% 92+8% (n=4)

Recoveries in DI Water

Actinide Column Cartridge

Am 72+13% (n=8) 84+6% (n=4)

U 90+2% (n=8) 84+9% (n=4)

Pu 96+2% (n=4) 70+5% (n=4)

Recoveries in Simulated Hanford Ground Water

Actinide Column Cartridge

Am 92% 79+8%

U 84% 78+9%

Pu 96% 82+4%

Recoveries in Synthetic Urine Samples

Actinide Column Cartridge

Am 72 + 13% 76 + 9%

U 89 + 6% 98 + 3%

Pu 96 + 2% 80 + 6%

Recoveries in Real Urine Samples

Actinide Column Cartridge

Am 75 + 8% 72 + 11%

U 82 + 9% 83 + 6%

Pu 94 + 4% 95 + 6%

PROCORADFrench Intercomparison SamplesSample U-234

dpm/LU-232(tracer)

1 2.94 + 0.38 79 %

2 2.79 + 0.31 89 %

3 2.66 + 0.33 83 %

Procoradvalue

2.81+ 0.28

Summary

• Eichrom Resin cartridges provide fast separation for actinides

• Good, reproducible and consistent recoveries achievable

•Rapid turn-around possible

Eichrom Cartridges

• Available in TRU, TEVA, UTEVA and Sr• Other Resins available by special order• 2 mL Resin volume• Standard S grade, 50-100 micron beads• Can be stacked using Luer connections• Standard syringe barrel used for reservoir• Individually labeled w/ lot number

Future Objectives

• Evaluate effect of faster flow rate on chemical recovery

• To test other matrices such as; fecal, soil and vegetation for actinides using Eichrom Resin cartridges

• To evaluate separation of Sr using Eichrom Sr Resin cartridges