1. The Determination of 99Tc in waste by ICPMS A First Look D. K
The Determination of 99Tc in waste by ICPMS A First Look D.K. Mann and V.F. Belt Y-12 National Security Complex BWXT Y-12 LLC Analytical Chemistry Organization 113C Union Valley Road, Oak Ridge, TN 37830, USA
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2. General Outline History Instrumentation and Theory
Use of Stable Re as a Tracer
Development of 99Tc Procedure
Testing and Sample Data
Benefits and Drawbacks
Future Work
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3. Introduction
99Tc produced by fission of 235U and 239Pu with approximately a 6% yield.
Main source in Environment is Nuclear weapons testing and Nuclear industries.
Pertechnetate ion (TcO4-1) highly mobile in ground and surface waters.
Pertechnetate ion localizes in the gastrointestinal tract and thyroid gland in humans and animals.
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4. Methods of Determination
Gas Proportional Counting
Liquid Scintillation Counting
Thermal Ionization Mass Spectrometry (TIMS)
Inductively Coupled Plasma Mass Spectrometry (ICPMS)
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5. Generation of ions in Plasma
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6. Schematic of ICP-MS ICP Spectrometry and its Applications, S. J
Schematic of ICP-MS ICP Spectrometry and its Applications, S.J. Hill, ed., Sheffied Press, 1999.
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7. Schematic of ICP-MS ICP Spectrometry and its Applications, S. J
Schematic of ICP-MS ICP Spectrometry and its Applications, S.J. Hill, ed.., Sheffied Press, 1999.
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8. VG PlasmaQuad II Main Unit
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9. VG PlasmaQuad ICPMS Cover Removed
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10. Nebulizer Setup Torchbox Cover Removed
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11. Gilson AutoSampler
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12. 99Tc Tracing: Limitations
Some sort of Chemical Separation needed (Liq.-Liq., Ion Exchange, Extraction Chrom.)
No stable isotope to perform gravimetric recoveries.
95mTc and 99mTc can be Gamma counted-short 1/2 life limits use. Must be counted separately on different instruments.
97Tc by TIMS and ICPMS-difficult to obtain.
Spiked and Unspiked samples-time and cost prohibitive.
Re and Ru-Behave similar to 99Tc, but may be present in sample
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13. Relative behavior of Tc and Re on TEVA resin (K. Tagami and S
Relative behavior of Tc and Re on TEVA resin (K. Tagami and S. Uchida, Analytica Chimica Acta, 405(2000), )
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14. 99Tc recovery in 2M HNO3
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15. 99Tc recovery in 4M HNO3
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16. Re recovery in 4M HNO3
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17. 99Tc Recovery in 6M HNO3
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18. D.I. Water Blank
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19. Typical Column Blank using TEVA resin
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20. Typical Sample Spectrum 4M HNO3
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21. Direct Injection of Sample into ICPMS
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22. 99Tc and 187Re Elution Curve from TEVA resin 4 Molar HNO3
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23. 99Tc and 187Re Elution Curve from TEVA resin 6 Molar HNO3
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24. 99Tc and 187Re Recovery from TEVA resin 6 Molar HNO3
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25. Drawbacks of ICPMS Method
High cost of Instrument (+200K).
High cost of supplies (Liq. Ar)
Need Highly Trained Chemist to Operate.
Instrument can be Finicky at times.
Not practical for small sample loads- unit needs to be run.
Need space for the unit plus a hood.
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26. Benefits of ICPMS Method
Tracer is Cheap and Available
Highly Automated (link with Gilson ASPEC).
Saves on resin ($60K per year).
Real time tracer analysis.
Rapid: 2-3 hours from start of instrument to finish (20 sample batch).
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27. Future Work Link unit to Gilson ASPEC units for more automation.
Apply to other isotopes.
Develop a “Dilute and Shoot” sample screen.
Try TEVA disks for environmental samples.
Try new 3 and 7 ml vessels from CEM
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28. CEM Micro Digestion Vessels 3 ml and 7 ml
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29. Conclusion
The use of Rhenium coupled with ICPMS analysis offers an excellent alternative for the analysis of 99Tc in waste samples.
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30. Conclusion(II)
Beware of strangers bearing gifts, especially if they are from another department.
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