1. Rapid Separation Methods for Bioassay Samples S. L. Maxwell, III and D. J. Fauth Westinghouse Savannah River Site

2. Advances in Rapid Column Extraction Significant advances in last 5 to 10 years Broad application in wide range of labs –Advancing analytical technology in process lab, bioassay lab, environmental lab, etc. Sample preparation required for wide range of analytical work –Remove matrix interferences prior to assay –Preconcentrate analyte Advantages –simpler, more selective than ion exchange –vacuum box speed improvements with cartridge technology –less waste, lower acidity, less hazardous

3. Improvements In Column Extraction 1990’s: Need to upgrade radiochemistry methods at SRS –Replace solvent extraction methods in CLAB-mixed waste –Upgrade analytical methods in SRS Bioassay Lab Rapid Separation Methods –Process laboratory (liquid and solid samples) –Bioassay laboratory (urine, fecal) –Environmental laboratory (soil)

4. Improvements In Column Extraction Rapid Column Extraction Applications at SRS –Process and waste analyses Pu, Np, U, Am, Th, Sr, Tc-99 for waste and process solutions at SRS (tandem methods) –E. Philip Horwitz, S.L. Maxwell et al., Analytica Chimica Acta, 310, 63, (1995). –S.L. Maxwell III, “Rapid Actinide-Separation Methods”, Radioactivity and Radiochemistry, 8, No 4, 36, (1997) UTEVA method for Pu/U oxides (Metal impurities assay on mixed oxide or actinide process solutions to remove U/Pu interferences and characterize materials by ICP-ES and ICP-MS, 1998-1999)

5. Improvements In Column Extraction –Process and waste analyses Trace actinides in mixed oxide materials (Np, Th, Am extraction for ICP-MS using TEVA, UTEVA-1998-1999) Simultaneous extraction of U, Pu for IDMS assay and isotopics in mixed oxides - (2000) –S.L. Maxwell and J. Satkowski, “Rapid Mass Spectrometry for Uranium and Plutonium”, Radioactivity and Radiochemistry Journal, Vol. 12, No 2, 2001

6. Recent Column Extraction Applications Column Extraction Applications at SRS –Soil and Fecal Sample Analyses Actinides in soil using Diphonix Resin-microwave digestion –S.L. Maxwell III and S. Nichols, “Actinide Recovery Method for Large Soil Samples”, Radioactivity and Radiochemistry, 11, No 4, 46, (2000) Pu, Am in fecal samples using Diphonix Resin-microwave digestion and TEVA+TRU Resin, (1999) –S.L. Maxwell and D. Fauth, “New Fecal Method for Pu and Am”, Journal of Radioanalytical and Nuclear Chemistry, Vol. 250, No. 1, 2001

7. Recent Column Extraction Applications Column Extraction Applications at SRS, contd. –Bioassay: urine Column extraction in Bioassay Lab for Pu, Np, Am, U plus Sr method using cartridge technology –S.L. Maxwell III and D. Fauth, “Rapid Column Extraction Methods for Urine”, Radioactivity and Radiochemistry, 11, No 3, 28, (2000)

9. Bioassay Urine Methods Improve chemical recoveries, improve Th-228 removal and reduce labor costs/rework –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 novel, 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

10. Urine Batch: Calcium Phosphate Precipitation

11. Pu, Np/Am, U, Sr on TEVA/TRU RESIN (URINE) Rinse 20 mL 3MHN0 3 Th Removal 3mL 9MHCI/30mL 8MHCI Pu Elution 30mL 0.10MHC1 - 0.05MHF - 0.1M NH 4 l 1)Adjust to 2.5MHN0 3 - 1M Al(NO 3 ) 3 2)0.05M Sulfamic Acid + 0.2M Ascorbic Acid 3)0.4 to 0.5M Sodium Nitrite Remove TRU cartridge: 1)Elute Am with 12mL 4M HCI 2)Elute U with 20mL 0.1M ammonium bioxalate 2mL TEVA Resin (50-100 um) 2.0mL TRU-Resin (50-100 um) Collect, evaporate, dissolve in 6M HNO 3 SR Resin Electrodeposition 4mls 0.02M H 2 SO 4 + 3mls 16M HN0 3 Evaporate/ash

12. TEVA+ TRU Stacked Column: Pu, Np, U, Am

13. TRU Cartridge: U, Am Stripping

14. SR Cartridge: Sr-90 Separation

15. TEVA Pu Tracer Recoveries 500 mL urine sample/ Pu-242 tracer= 1.25 dpm / One TEVA Column Fe+AA/+NO 2 %Recovery (CeF 3 microprecipitation) % Recovery (Electroplating* ) 1)1101) 84.4 2) 93.32) 72.4 3)92.63) 69.3 4) 95.24)69.6 5) 101.55) 79.8 6) 99.36) 84.5 7) 97.7 7) 79.1 8) 115.48) 85.5 9) 107.99) 84.8 10)106.810)77.0 11)101.611) 82.5 12)102.6 Avg. =102.0% (  7.0% @1s) Avg. = 79.0 (  6.2% @1s) *Add 4 mL 0.02M H2SO4 to enhance F removal during solution cleanup for plating

16. TEVA- Np-237, Pu-236 Recoveries 500 mL urine sample/ Np-237 spike= 1.40 dpm/Pu-236=0.425 dpm Single TEVA column (CeF 3 microprecipitation) % Pu-236% Np-237 Recovery Recovery 1)94.0*** 2) 92.5*** 3)101*** 4) 100*** 5) 111*** 6) 91.088.1 7) 91.9 86.7 8) 105 102.9 9) 109 102.0 10)88.9 94.2 Avg. =98.4% (  7.9% @1s) Avg. = 94.8% (  7.6% @1s) Additional bias comparison on 24 samples: -1.49% +/- 6% estimate of bias

17. Bioassay Lab Alpha Counters

18. Bioassay Lab Gas Proportional Counters:Sr

23. TRU Resin -Am Tracer Recoveries 500 mL urine sample/ Am-243 tracer= 1.55 dpm / TRU cartridge after TEVA SA+AA/+NO 2 / 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% (  10.6% @1s)

28. Recent Advances In Urine Method Use scrubbed U-232 tracer to minimize Th-228 daughter added and eliminate need for 2nd TEVA column cleanup when uranium analyzed with Pu, Np, Am, Sr Add boric acid to eliminate adverse effect of trace fluoride on electroplating/increased tracer recoveries

29. Th-228 In-Growth After Removal from U-232

31. Microwave Digestion of Diphonix: Fecal Method

32. Pu, Am ON TEVA + TRU RESIN (FECAL METHOD)

33. 2

34. Pu on TEVA RESIN (2nd Column to Remove all Th-228) Redissolve in 7.5mL 3M HN0 3 + 1mL 2.5M Al(NO 3 ) 3 Add 0.5mL 1.5M Ferrous Sulfate + 1mL 1.5M Ascorbic Acid Add 1mL 3.5M Sodium Nitrite Add 1mL 16M Nitric Acid Th Removal 3mL 9MHCI/7mL 8MHCI Rinse 10mL 3MHN0 3 Pu Elution 20 mL 0.10MHC1 - 0.05MHF - 0.1M NH 4 l 1mL TEVA Resin

37. Summary New rapid column extraction methods have greatly improved radiochemical separation technology –process lab support –bioassay lab applications –environmental lab work Vacuum-enhanced column and cartridge extraction methods have enhanced lab capabilities –simpler, faster, less rework, less waste Rapid extraction technology continues to advance at the frontier of radioanalytical chemistry