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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. Improvements In Column Extraction . 1990s: Need to upgrade radiochemistry methods at SRS Methods developed and implemented

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rapid extraction methods for the process laboratory

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

improvements in column extraction
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
improvements in column extraction3
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)
improvements in column extraction4
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)
uteva pu u separation for idms assay by tims
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
uteva pu u separation for idms assay by tims6
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
np th in mixed oxide by icp ms
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
uteva pu u removal for metals assay
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
uteva pu u removal method
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

uteva pu u removal method for impurities assay
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
average column spike recoveries icp aes
Average Column Spike RecoveriesICP-AES

Ag 92 Hf 84 Se 101

Al 99 Hg 69 Si 151

As 90 K 87 Ta 69

B 100 La 100 V 98

Ba 100 Li 97 W 106

Be 98 Mg 105 Zn 101

Ca 94 Mo 98 Zr 63

Cd 96 Na 105

Ce 103 Nb 99

Cr 102 Ni 101

Cu 98 P 161

Fe 106 Pb 84

Ga 104 S 97

Element % Recovery Element % Recovery Element % Recovery

average column spike recoveries icp ms
Average Column Spike RecoveriesICP-MS

Ag 106 Hf 90 Se 87

Al 101 Hg 77 Si 132

As 88 K 102 Ta 84

B 89 La 108 V 104

Ba 106 Li 101 W 113

Be 90 Mg 103 Zn 91

Ca NA Mo 101 Zr 63

Cd 94 Na 98

Ce 108 Nb 98

Cr 103 Ni 103

Cu 106 P 154

Fe 106 Pb 99

Ga 101 S NA

Element % Recovery Element % Recovery Element % Recovery

analysis of crm 124 uranium oxide standards
Analysis of CRM-124 Uranium Oxide Standards

Al 102 105 (81-120) -3%

Be 11.6 12.5 (10-17) -7%

Cr 55.4 52 (50-64) +6%

Mg 52.4 51 (37-86) +3%

Mo 53.7 50 (30-50) +7%

Na 230 200 (189-252) +15%

Ni 106 102 (92-158) +4%

V 24.2 25 (23-30) -3%

W 105 100 (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

Measured Ref. Prepared Value/

Element (ppm) dc arc range (ppm)%Difference

am in mixed oxide by icp ms
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
summary
Summary
  • Process column methods
    • Faster and more rugged
    • Reduced labor costs
    • Better accuracy and precision
    • Reduced rework
    • No mixed waste solvents
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