Recent Improvements in Rapid Column Separation Methods at SRS S. L. Maxwell, III, D. J. Fauth, R. C. Henderson, J. J. Smiley, S. R. Johnson Westinghouse Savannah River Site

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

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)

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

Urine Batch: Calcium Phosphate Precipitation

Pu, Np/Am, U, Sr on TEVA/TRU RESIN (URINE) Rinse 20 mL 3MHN0 3 Th Removal 3mL 9MHCI/30mL 8MHCI Pu Elution 30mL 0.10MHC MHF - 0.1M NH 4 l 1)Adjust to 2.5MHN M 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 ( um) 2.0mL TRU-Resin ( um) Collect, evaporate, dissolve in 6M HNO 3 SR Resin Electrodeposition 4mls 0.02M H 2 SO 4 + 3mls 16M HN0 3 Evaporate/ash

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

TRU Cartridge: U, Am Stripping

SR Cartridge: Sr-90 Separation

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) ) 93.32) )92.63) ) 95.24)69.6 5) ) ) 99.36) ) ) ) ) ) ) ) ) ) ) )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 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) ) ) ) ) Avg. =98.4% (  Avg. = 94.8% (  Additional bias comparison on 24 samples: -1.49% +/- 6% estimate of bias

Bioassay Lab Alpha Counters

Bioassay Lab Gas Proportional Counters:Sr

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) ) ) ) ) ) ) ) ) )94.7 Avg. =96.9% ( 

Microwave Digestion of Diphonix: Fecal Method

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

2

Pu on TEVA RESIN (2nd Column to Remove all Th-228) Redissolve in 7.5mL 3M HN mL 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 0.10MHC MHF - 0.1M NH 4 l 1mL TEVA Resin

UTEVA Pu/U Removal for Metals Assay at Savannah River UTEVA Resin (diamylamylphosphonate) –Recovers all impurities except Au* –Zr, Ta, Hf, Nb require dilute HF in column load (and/or rinse) solution –Handles Pu, U or Pu/U mixtures –Large 10 mL columns remove 200 mg or more of Pu/U * Au done by dilute HCL-HF cation method

UTEVA Pu/U Removal Method for Impurities Assay Glove box separation for Pu materials Load solution: 10 mL 8 M HNO3-0.04M HF Column rinse: mLs 8M HNO3 (optional with HF) Adjust to 25 or 30 mL in graduated tube Pu/U recovery from resin: 20 mL 0.1M HCl- 0.05M HF

Average Column Spike Recoveries ICP-MS Element % Recovery Element % Recovery Element % Recovery Ag106 Hf90 Se 87 Al101 Hg77 Si 132 As88 K102Ta 84 B89La108V 104 Ba106Li101W 113 Be90Mg103Zn 91 CaNAMo101Zr 63 Cd94Na98 Ce108Nb98 Cr103Ni103 Cu 106P154 Fe106Pb99 Ga101SNA

Process Lab Improvements Process samples to support HEU Blenddown processing Improvements: –Pu and Np are key product specification measurements –Pu-236 tracer for Pu and Np on TEVA resin in HEU and LEU process solutions –1 mL TEVA cartridges to ensure total Th-228 removal (separated twice on TEVA) –use Ti (III) reductant in Pu strip from TEVA

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