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

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

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 0.10MHC1 - 0.05MHF - 0.1M NH4l 4mls 0.02M H2SO4 + 3mls 16M HN03 2mL TEVA Resin (50-100 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 (50-100 um) Collect, evaporate, dissolve in 8M HNO3 SRS Resin

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 0.10MHC1 - 0.05MHF - 0.1M NH4l 1mL TEVA Resin

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) 93.3 2) 72.4 3) 92.6 3) 69.3 4) 95.2 4) 69.6 5) 101.5 5) 79.8 6) 99.3 6) 84.5 7) 97.7 7) 79.1 8) 115.4 8) 85.5 9) 107.9 9) 84.8 10) 106.8 10) 77.0 11) 101.6 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

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-237 Recovery Recovery 1) 94.0 *** 2) 92.5 *** 3) 101 *** 4) 100 *** 5) 111 *** 6) 91.0 88.1 7) 91.9 86.7 8) 105 102.9 9) 109 102 10) 88.9 94.2 Avg. = 98.4% Avg. = 94.8%

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) 93.2 2) 92.1 3) 107.4 4) 70.3 5) 102.4 6) 103.0 7) 100.2 8) 103.3 9) 102.6 10) 94.7 Avg. = 96.9%

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%

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%)

Accuracy on Spiked Urine Samples U-234 U-238 U-235 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%)

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

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

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

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

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

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 0.10MHC1 - 0.05MHF - 0.1M NH4l 2mL TEVA Resin (50-100 um) 4mls 0.02 H2S04/3mLs 16MHN03 evaporate ash H2O2 1mL 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 (50-100 um)

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 0.10MHC1 - 0.05MHF - 0.1M NH4l 1mL TEVA Resin

TEVA+TRU Pu/Am Tracer Recoveries Fecal samples: 1.5-4 grams ash/Pu-242 spike = 1.26 dpm TEVA column+ 2nd 1 mL TEVA column %Pu-242 Recovery %Am-243 Recovery Fecal blank 1A 75.3 91.5 Fecal blank 1B 68.5 103.1 Fecal blank 2 72.1 81.5 Fecal blank 3 A 75.6 89.2 Fecal blank 3 B 79.3 95.8 Fecal blank 4 78.4 100.8 Avg. 74.9 93.7 Column Reagent blank 74.4 90.8 blank 82.8 89.8 Avg. 78.6 90.3

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

Assay of of DOE-RESL Fecal Standards Pu-239 Am-241 (picocuries) % Bias (picocuries) %Bias 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%

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 -------- 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%)

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%)

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%)

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