1. 00J01587-01.ppt Rapid Extraction Methods for the Process Laboratory S. L. Maxwell, III V. D. Jones S. T. Nichols J. Satkowski M. A. Bernard Westinghouse Savannah River Site

2. 00J01587-01.ppt Improvements In Column Extraction 1990s: Need to upgrade radiochemistry methods at SRS Methods developed and implemented Rapid Column Extraction Applications at SRS –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). –TEVA+ UTEVA+ TRU sequential methods –Applied primarily to waste tank samples

3. 00J01587-01.ppt Improvements In Column Extraction Upgraded process laboratory methods in 1996 –Pu and Np by alpha spectrometry –U by laser phosphorescence –Pu and U actinide isotopics—TIMS S.L. Maxwell III, “Rapid Actinide-Separation Methods”, Radioactivity and Radiochemistry, 8, No 4, 36, (1997) –Pu-TEVA (valence-ferrous sulfate/sodium nitrite) –Np-TEVA (valence-ferrous sulfamate + ascorbic acid) –U on UTEVA (valence-ferrous sulfamate) –Dual column TEVA+ UTEVA cartridge (valence-ferrous sulfate/sodium nitrite)

4. 00J01587-01.ppt Improvements In Column Extraction Expanded to characterization of metals/oxides: –UTEVA method for Pu/U oxides (Impurity assay in mixed oxide or actinide process solutions—1998-1999) –Trace actinides in mixed oxide materials (Np, Th, Am extraction for ICP-MS using TEVA, UTEVA—1998-1999) –New UTEVA method for Pu and U-Isotope Dilution Mass spectrometry in mixed oxides (strip Pu separately using 3M HNO3- 0.2MHF) -(2000)

5. 00J01587-01.ppt UTEVA Pu/U Separation for IDMS Assay by TIMS Currently: Pu isotopics on TEVA; U on UTEVA For mixed U/Pu solutions requiring assay/isotopics, combine on UTEVA Approach: –Load on UTEVA –Strip Pu first using 3M HNO3-0.2M HF, then strip U with 0.02M HNO3-0.005M HF. –Reduces labor costs and improves productivity

6. 00J01587-01.ppt UTEVA Pu/U Separation for IDMS Assay by TIMS 1 mL UTEVA resin U-233 (140 ug) and Pu-244 (0.7 ug) spiked samples Load solution: 5 mL 2.5 M HNO3-0.5M Al (NO3) 3 Valence adjustment to Pu (IV) with ferrous sulfate/nitrite Column rinse: 13 mL 3M HNO3 Pu strip: 5 mls 3M HNO3 -0.2M HF (ash well to remove F) U strip: 5 mL 0.02M HNO3 -0.005M HF

7. 00J01587-01.ppt Np, Th in Mixed Oxide by ICP-MS Material dissolution by microwave Dilution in glove box; separation in radiohood Np and Th on 1 mL TEVA resin –Load solution 2.5M HNO3-0.5M Al(NO3) 3 –Reduce Pu to Pu+3: ferrous sulfamate + ascorbic acid –3M HNO3 rinse –Pu +3 / U +6 not retained on TEVA –Strip Np+Th together using 5 mL 0.02M HNO3-0.005M HF Use 2nd TEVA column to remove nearly all U+Pu Dilute and analyze by ICP-MS 95%+ recovery

8. 00J01587-01.ppt UTEVA Pu/U Removal for Metals Assay Background AG MP-1 Anion resin for Pu removal prior to ICP-AES/MS of impurities in metal/oxides to removal spectral interference: –Problem: at least partial retention of Au, Ag, Pt, Ir, Pd, Nb, Tl, La, Ce and Ta on anion resin –Increased need to analyze mixed Pu/U materials requiring Pu/U removal UTEVA resin offers improved impurity recovery and removes both Pu and U

9. 00J01587-01.ppt UTEVA Pu/U Removal Method 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

10. 00J01587-01.ppt 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: 14-19 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 Note: –No HF in rinse to enhance Pu retention; still adequate recovery of Zr, Ta, Hf, Nb –May increase HF with U only to increase Ta, etc., but minimize to minimize Si background at ICP-torch due to HF –Load solution can be larger –HF in rinse may be necessary if HF is less in load solution

11. 00J01587-01.ppt Average Column Spike Recoveries ICP-AES Ag92 Hf84 Se101 Al99 Hg69 Si151 As90 K87Ta69 B100La100V98 Ba100Li97W106 Be98Mg105Zn101 Ca94Mo98Zr63 Cd96Na105 Ce103Nb99 Cr102Ni101 Cu 98P161 Fe106Pb84 Ga104S97 Element% Recovery Element % RecoveryElement% Recovery

12. 00J01587-01.ppt Average Column Spike Recoveries ICP-MS Ag106Hf90 Se87 Al101Hg77 Si132 As88K102Ta84 B89La108V104 Ba106Li101W113 Be90Mg103Zn91 CaNAMo101Zr63 Cd94Na98 Ce108Nb98 Cr103Ni103 Cu106P154 Fe106Pb99 Ga101SNA Element% Recovery Element% Recovery Element % Recovery

13. 00J01587-01.ppt Analysis of CRM-124 Uranium Oxide Standards Al102105 (81-120)-3% Be11.612.5 (10-17)-7% Cr55.4 52 (50-64)+6% Mg52.4 51 (37-86)+3% Mo53.7 50 (30-50)+7% Na230 200 (189-252)+15% Ni 106102 (92-158)+4% V 24.2 25 (23-30)-3% W105 100 (86-95)+5% Zn 110 102 (75-115)+8% Zr 108 100 (67-100)+8% measured = single solution analyzed once by ICP-AES and ICP-MS MeasuredRef. Prepared Value/ Element (ppm) dc arc range (ppm) %Difference

14. 00J01587-01.ppt Am in Mixed Oxide by ICP-MS Use solution (8M HNO3) from initial UTEVA resin separation (10 ml resin) for metal impurities –No retention of Am on UTEVA resin Remove traces of uranium and plutonium using 2 ml UTEVA column –2 mL aliquot –8 mL 8M HNO3 column rinse Dilute to low acid Analyze by ICP-MS

15. 00J01587-01.ppt Summary Process column methods –Faster and more rugged –Reduced labor costs –Better accuracy and precision –Reduced rework –No mixed waste solvents