1. New Extraction Methods for Urine and Fecal Samples
Sherrod L. Maxwell
David J. Fauth
Savannah River Site

2. 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

4. Pu, Np/Am, U, Sr on TEVA/TRU Resin (Urine)
1) Adjust to 2.5MHN03 - 1M Al(NO3)3
2) 0.05M sulfamic acid + 0.2M ascorbic acid
3) 0.4 to 0.5M sodium nitrite
Th Removal
3mL 9MHCI/30mL
8MHCI
Rinse
15mL 3MHN03
Pu Elution
30mL
0.10MHC MHF - 0.1M NH4l
4mls 0.02M H2SO4 + 3mls 16M HN03
2mL TEVA Resin
( um)
Evaporate
2nd TEVA
Column
Remove TRU cartridge:
1) Elute Am with
12mL 4M HCI
2) Elute U with
20mL 0.1M ammonium
bioxalate
2.0mL TRU-Resin
( um)
Collect, evaporate, dissolve in 8M HNO3
SRS Resin

5. 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 Removal
2mL 9MHCI/8mL
8MHCI
Rinse
10mL 3MHN03
Pu Elution
15mL
0.10MHC MHF - 0.1M NH4l
1mL TEVA Resin

6. TEVA Pu Tracer Recoveries
500 mL urine sample/ Pu-242 tracer = 1.25 dpm/One TEVA Column Fe+AA/+NO2
%Recovery % Recovery
(CeF3 microprecipitation) (Electroplating*)
1) 110 1) 84.4
2) ) 72.4
3) ) 69.3
4) ) 69.6
5) ) 79.8
6) ) 84.5
7) ) 79.1
8) ) 85.5
9) ) 84.8
10) ) 77.0
11) ) 82.5
12) 102.6
Avg. = 102.0% Avg. = 79.0
*Add 4 mL 0.02M H2SO4 to enhance F removal during solution cleanup for plating

7. TEVA- Np-237, Pu-236 Recoveries
500 mL urine sample/Np-237 spike = 1.40 dpm/Pu-236 = dpm
SA+AA/+NO2/Single TEVA column (CeF3 microprecipitation)
% Pu-236 % Np-237
Recovery Recovery
1) *** 2) *** 3) 101 *** 4) *** 5) *** 6) )
8) )
10)
Avg. = 98.4% Avg. = 94.8%

10. 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) 2) 3) 4) 5) 6) 7) 8) 9)
10) 94.7
Avg. = 96.9%

11. TRU Resin-U Tracer Recoveries
500 mL urine sample/U-232 tracer = 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)
3) 85.6 4)
5) 90.6
6) 83.1
7) 57.7
8) 81.0
9) 80.4
10) 93.3
Avg. = 84.7%

12. Accuracy on Spiked Urine Samples
Pu-238 Pu-239 Am-241 Sr-90
Levels dpm/L
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 (N=8) (N=8) (N=23) (N=4)
DOELAP criteria (Bias: -25% to +50%)

13. Accuracy on Spiked Urine Samples
U-234 U-238 U-235
Levels
dpm/L dpm/L
Number Samples N=4 N=4
Average Bias +7.8% +1.5%
Blanks (N=12) (N=10) (N=12)
DOELAP criteria (Bias: -25% to +50%)

14. 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

15. New Approach Old method: New approach:
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

16. 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

17. 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
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

18. 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

19. Pu, Am on TEVA + TRU Resin (Fecal Method)
Adjust to 2.5MHN03 -1M Al(NO3)3
1) 0.1M ferrous sulfate
2) 0.25M sodium nitrite
Th Removal
3mL 9MHCI/30mL
8MHCI
Rinse
15 to 20mL 3MHNO3
Pu Elution
30mL
0.10MHC MHF - 0.1M NH4l
2mL TEVA Resin
( um)
4mls 0.02 H2S04/3mLs 16MHN03
evaporate ash H2O mL
TEVA column to ensure
complete Th-288 removal
- evaporate
- redissolve in 3M HNO3
- add sulfamic acid + ascorbic acid
Am Elution
3mL 9MHCI/15mL -4M HCI
Rinse
1) 5mL
2.5M HNO3-0.1M
ascorbic acid
2) 5mL 3M HNO3
0.1M NaNO2
3) 10mL 3M HNO3
2ml TRU resin
( um)

20. 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 Removal
2mL 9MHCI/8mL
8MHCI
Rinse
10mL 3MHN03
Pu Elution
15mL
0.10MHC MHF - 0.1M NH4l
1mL TEVA Resin

21. TEVA+TRU Pu/Am Tracer Recoveries
Fecal samples: grams ash/Pu-242 spike = 1.26 dpm
TEVA column+ 2nd 1 mL TEVA column
%Pu-242 Recovery %Am-243 Recovery
Fecal blank 1A
Fecal blank 1B
Fecal blank
Fecal blank 3 A
Fecal blank 3 B
Fecal blank
Avg
Column Reagent
blank
blank
Avg

22. 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

23. Assay of of DOE-RESL Fecal Standards
Pu Am-241
(picocuries) % Bias (picocuries) %Bias
DOE-RESL values
SR-194 #
SR-194 #
Avg % %
SR-234 #
SR-234 #
Avg % %

24. Plutonium Results on Leached EML QAP Soil Samples
Smp. Wt. Pu-242 Tracer Pu-238 Pu-239 Recovery (dpm/g) (dpm/g)
9403 EML Value
9.957g 90%
10.100g 80%
14.980g 97%
Avg. 89% (-2.8%) (-2.4%)

25. 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
10.00g 73%
10.00g 82%
10.00g 85%
10.00g 80%
Avg. 80% (-10%) 1.42 (+11%)

26. Am Results on Fused EML QAP Soil Samples
Smp. Wt. Am-243 Tracer Am Recovery (dpm/g)
9609 EML Value
10.00g 84% 0.94
10.00g 87% 0.83
10.00g 73% 0.95
Avg. 80% 0.90 (+11%)

27. 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