00J 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

00J 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

00J 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)

00J 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— ) –Trace actinides in mixed oxide materials (Np, Th, Am extraction for ICP-MS using TEVA, UTEVA— ) –New UTEVA method for Pu and U-Isotope Dilution Mass spectrometry in mixed oxides (strip Pu separately using 3M HNO3- 0.2MHF) -(2000)

00J 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 HNO M HF. –Reduces labor costs and improves productivity

00J 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 HNO M HF

00J 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 HNO M HF Use 2nd TEVA column to remove nearly all U+Pu Dilute and analyze by ICP-MS 95%+ recovery

00J 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

00J 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

00J 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: 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

00J 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

00J 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

00J ppt Analysis of CRM-124 Uranium Oxide Standards Al (81-120)-3% Be (10-17)-7% Cr (50-64)+6% Mg (37-86)+3% Mo (30-50)+7% Na ( )+15% Ni (92-158)+4% V (23-30)-3% W (86-95)+5% Zn (75-115)+8% Zr (67-100)+8% measured = single solution analyzed once by ICP-AES and ICP-MS MeasuredRef. Prepared Value/ Element (ppm) dc arc range (ppm) %Difference

00J 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

00J ppt Summary Process column methods –Faster and more rugged –Reduced labor costs –Better accuracy and precision –Reduced rework –No mixed waste solvents