00J01587-02.ppt

New Extraction Methods for Urine and Fecal Samples

Sherrod L. Maxwell

David J. Fauth

Savannah River Site

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Bioassay Urine Methods

• Improve chemical recoveries, improve Th-228 removal reduce acid waste and labor costs/rework

• Replace anion exchange methods and use vacuum-enhanced extraction chromatography– Pu (Np when Pu-236 tracer used) on TEVA resin

– Pu, Np, U, Am, Sr

• Single two cartridge TEVA/TRU column plus SR resin

• No iron in urine allows single stacked TEVA+TRU column

• Pu, Np on TEVA; U, Am on TRU cartridge in stacked column

• Sr collected, evaporated, redissolved, separated on SR resin column

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Pu, Np/Am, U, Sr on TEVA/TRU Resin (Urine)

Rinse15mL 3MHN03

Th Removal3mL 9MHCI/30mL

8MHCI

Pu Elution30mL

0.10MHC1 - 0.05MHF - 0.1M NH4l

1) Adjust to 2.5MHN03 - 1M Al(NO3)3

2) 0.05M sulfamic acid + 0.2M ascorbic acid3) 0.4 to 0.5M sodium nitrite

Remove TRU cartridge:1) Elute Am with

12mL 4M HCI2) Elute U with

20mL 0.1M ammoniumbioxalate

2mL TEVA Resin(50-100 um)

2.0mL TRU-Resin(50-100 um)

Collect, evaporate, dissolve in 8M HNO3SRS Resin

2nd TEVAColumn

4mls 0.02M H2SO4 + 3mls 16M HN03

Evaporate

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Pu on TEVA Resin (Urine or Fecal)

(2nd Column to Remove all Th-228)

•Redissolve in 7.5mL 3M HN03 + 1mL 2.5M Al(NO3)3

•Add 0.5mL 1.5M ferrous sulfate + 1mL 1.5M ascorbic acid•Add 1mL 3.M sodium nitrite•Add 1mL 16M nitric acid

Th Removal2mL 9MHCI/8mL

8MHCIRinse

10mL 3MHN03

Pu Elution15mL

0.10MHC1 - 0.05MHF - 0.1M NH4l

1mL TEVA Resin

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TEVA Pu Tracer Recoveries

• 500 mL urine sample/ Pu-242 tracer = 1.25 dpm/One TEVA Column Fe+AA/+NO2

*Add 4 mL 0.02M H2SO4 to enhance F removal during solution cleanup for plating

1) 110 1) 84.42) 93.3 2) 72.43) 92.6 3) 69.34) 95.2 4) 69.65) 101.5 5) 79.86) 99.3 6) 84.57) 97.7 7) 79.18) 115.4 8) 85.59) 107.9 9) 84.810) 106.8 10) 77.011) 101.6 11) 82.512) 102.6

Avg. = 102.0% Avg. = 79.0

%Recovery % Recovery

(CeF3 microprecipitation) (Electroplating*)

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TEVA- Np-237, Pu-236 Recoveries

• 500 mL urine sample/Np-237 spike = 1.40 dpm/Pu-236 = 0.425 dpm

• SA+AA/+NO2/Single TEVA column (CeF3 microprecipitation)

% Pu-236 % Np-237Recovery Recovery

1) 94.0 *** 2) 92.5 *** 3) 101 *** 4) 100 *** 5) 111 *** 6) 91.0 88.17) 91.9 86.78) 105 102.99) 109 10210) 88.9 94.2

Avg. = 98.4% Avg. = 94.8%

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TRU Resin-Am Tracer Recoveries

• 500 mL urine sample/Am-243 tracer = 1.55 dpm/TRU cartridge after TEVA

• SA+AA/+NO2 /load TEVA and TRU at same time/remove TRU

cart./elute Am

% Am-243 Recovery (Electroplating*)

1) 93.22) 92.13) 107.44) 70.35) 102.46) 103.07) 100.28) 103.39) 102.610) 94.7

Avg. = 96.9%

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TRU Resin-U Tracer Recoveries

• 500 mL urine sample/U-232 tracer = 0.554 dpm/TRU cartridge after TEVA

• SA+AA/+NO2 /load TEVA and TRU at same time/remove TRU cart./elute U

% U-232 Recovery (Electroplating*)

1) 97.9

2) 74.1

3) 85.6

4) 102.9

5) 90.6

6) 83.1

7) 57.7

8) 81.0

9) 80.4

10) 93.3

Avg. = 84.7%

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Accuracy on Spiked Urine Samples

Pu-238 Pu-239 Am-241 Sr-90

Levels 0.145-4.95 0.022-3.62 0.55-3.5 dpm/L 5.4-188 dpm/L dpm/L dpm/L picoCi/L

Number Samples N=12 N=12 N=7 N=6

Bias -14.7% +12.4% -3.4% -4.8%

Blanks 0.016 (N=8) 0.012 (N=8) 0.007 (N=23) -0.05 (N=4)

DOELAP criteria (Bias: -25% to +50%)

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Accuracy on Spiked Urine Samples

Levels 0.197-2.04 0.147-3.02

dpm/L dpm/L

Number Samples N=4 N=4

Average Bias +7.8% +1.5%

Blanks 0.008 (N=12) 0.012 (N=10) -0.001 (N=12)

DOELAP criteria (Bias: -25% to +50%)

U-234 U-238 U-235

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Need for Improved Fecal Analysis for Pu and Am at SRS

• Background– SRS incident in FB-Line

– Need for improved fecal analysis

• Complete dissolution of any plutonium oxide present

• Effective Th-228 removal

– Problems with microwave vessels

• Corrected pressure release valve problems

• Completed FB-Line incident samples

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New Approach

• Old method:– Residual undissolved solids in final nitric acid solution

– Solids contained some activity

• New approach: – Continue to use HNO3-HF dissolution/multiple digestion

– Apply diphonix resin technology

– Used successfully for large soil samples

– Allows loading from HCl-HF solutions

– Digest Diphonix using SRS microwave method

– Apply Eichrom sequential column method

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Method Details

• Microwave digestion of Diphonix resin

– Microwave to 190C for 15 minutes in 10 mL 16M HNO3

– Change disk & microwave to 200C for 20 minutes in 10 mL 16M HNO3

– Change disk & microwave to 215C for 25 minutes in 10 mL 16M HNO3

– Add 3.5 mL 30wt% H2O2 and microwave to 21OC for 10 minutes in

10 ml 16M HNO3

• Final wet ashing of resin– Ash with 30wt% H2O2 four times

– Ash with HNO3 + H2O2 one time, or until does not get any whiter

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Method Details

• Preparation for Pu, Am column separation

– Dissolve in 6 mLs of 5M to 6M HNO3

– Add 6 mLs 2 to 2.5M aluminum nitrate

– Solution ready for TEVA + TRU resin column extraction

• Preparation for Pu, Am column separation– Valence adjustment for Pu

1) Add 1 mL 1.5M ferrous sulfate + 1 mL 1.5M ascorbic acid, wait 3 min.

2) Add 1 mL 3.5M sodium nitrite

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Method Details

• Separate Pu using TEVA column– Th removal 9M HCl+8M HCl

– Use 2nd 1 mL TEVA column to remove all Th-228

– High retention/good clean-up

• Separate Am using TRU column – Collect load plus rinse from 1st TEVA column

– Evaporate to dryness

– Redissolve in 15 mls 3 M HNO3

– Add 2 mLs 1.5M sulfamic acid + 5 mls 1.5M ascorbic acid

– Load to TRU resin

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Pu, Am on TEVA + TRU Resin (Fecal Method)

2ml TRU resin(50-100 um)

4mls 0.02 H2S04/3mLs 16MHN03

evaporate ash H2O2 1mL

TEVA column to ensure complete Th-288 removal

Am Elution3mL 9MHCI/15mL -4M HCI

Rinse15 to 20mL 3MHNO3

Th Removal3mL 9MHCI/30mL

8MHCI

Pu Elution30mL

0.10MHC1 - 0.05MHF - 0.1M NH4l

Adjust to 2.5MHN03 -1M Al(NO3)3

1) 0.1M ferrous sulfate2) 0.25M sodium nitrite

Rinse1) 5mL

2.5M HNO3-0.1Mascorbic acid

2) 5mL 3M HNO3

0.1M NaNO2

3) 10mL 3M HNO3

2mL TEVA Resin(50-100 um)

- evaporate- redissolve in 3M HNO3

- add sulfamic acid + ascorbic acid

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Pu on TEVA Resin (Urine or Fecal)(2nd Column to Remove all Th-228)

• Redissolve in 7.5mL 3M HN03 + 1mL 2.5M Al(NO3)3

• Add 0.5mL 1.5M ferrous sulfate + 1mL 1.5M ascorbic acid• Add 1mL 3.M sodium nitrite• Add 1mL 16M nitric acid

Th Removal2mL 9MHCI/8mL

8MHCIRinse

10mL 3MHN03

Pu Elution15mL

0.10MHC1 - 0.05MHF - 0.1M NH4l

1mL TEVA Resin

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TEVA+TRU Pu/Am Tracer Recoveries

Fecal blank 1A 75.3 91.5 Fecal blank 1B 68.5 103.1 Fecal blank 2 72.1 81.5Fecal blank 3 A 75.6 89.2Fecal blank 3 B 79.3 95.8Fecal blank 4 78.4 100.8

Avg. 74.9 93.7Column Reagent blank 74.4 90.8Column Reagent blank 82.8 89.8

Avg. 78.6 90.3

Fecal samples: 1.5-4 grams ash/Pu-242 spike = 1.26 dpmTEVA column+ 2nd 1 mL TEVA column

%Pu-242 Recovery %Am-243 Recovery

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Method Validation

• Analysis of multiple sample blanks– Complete dissolution

– High tracer recovery

– Good Th-228 removal

• Analysis of artificial fecal sample spiked with Pu oxide from RESL-Idaho– Test plan to validate versus known Pu levels

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Assay of of DOE-RESL Fecal Standards

DOE-RESL values 2.18 2.76

SR-194 #1 1.860 2.405

SR-194 #2 1.841 2.608

Avg. 1.850 -15.1% 2.507 -9.2%

SR-234 #1 2.062 2.488

SR-234 #2 2.139 2.335

Avg. 2.101 -1.4% 2.411 -10.7%

Pu-239 Am-241(picocuries) % Bias (picocuries) %Bias

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Plutonium Results on Leached EML QAP Soil Samples

Smp. Wt. Pu-242 Tracer Pu-238 Pu-239Recovery (dpm/g) (dpm/g)

9403 EML Value -------- 0.672 0.216

9.957g 90% 0.664 0.200

10.100g 80% 0.663 0.223

14.980g 97% 0.632 0.211

Avg. 89% 0.653 (-2.8%) 0.211 (-2.4%)

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Pu Results on Fused EML QAP Soil Samples

Smp. Wt. Pu-242 Tracer Pu-238 Pu-239

Recovery (dpm/g) (dpm/g)

9609 EML Value -------- 0.068 1.31

10.00g 73% 0.080 1.47

10.00g 82% 0.047 1.43

10.00g 85% 0.053 1.41

10.00g 80% 0.063 1.39

Avg. 80% 0.061 (-10%) 1.42 (+11%)

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Am Results on Fused EML QAP Soil Samples

Smp. Wt. Am-243 Tracer Am-241 Recovery (dpm/g)

9609 EML Value -------- 0.81

10.00g 84% 0.94

10.00g 87% 0.83

10.00g 73% 0.95

Avg. 80% 0.90 (+11%)

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Summary

• Urine– Pu, Np and Am, U on two cartridge TEVA-TRU column with Sr-90

on SR resin after evaporation

– High recovery/good Th-228 removal

– Rapid column methods for urine will result in significant time/cost savings/waste reduction

• Fecal– New fecal method dissolves Pu oxide using HNO3 -HF

– Diphonix method has improved fecal analysis at SRS

• total dissolution

• remove Pu, Am from HCl-HF sample solutions

• excellent Th-228 removal/good results on DOE-RESL samples