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 DISCLAIMER This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, make any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information , apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. COPYRIGHT NOTICE The submitted manuscript has been authored by a subcontractor of the U. S. Government under contract DE‑AC05‑84OR21400. Accordingly, the U. S. Government retains a paid‑up, nonexclusive, irrevocable, worldwide license to publish or reproduce the published form of this contribution, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, or allow others to do so, for U. S. Government purposes.

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 Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

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. Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

Methods of Determination Gas Proportional Counting Liquid Scintillation Counting Thermal Ionization Mass Spectrometry (TIMS) Inductively Coupled Plasma Mass Spectrometry (ICPMS) Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

Generation of ions in Plasma Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

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. Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

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. Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

VG PlasmaQuad II Main Unit Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

VG PlasmaQuad ICPMS Cover Removed Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

Nebulizer Setup Torchbox Cover Removed Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

Gilson AutoSampler Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

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 Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

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), 227-229) Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

99Tc recovery in 2M HNO3 Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

99Tc recovery in 4M HNO3 Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

Re recovery in 4M HNO3 Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

99Tc Recovery in 6M HNO3 Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

D.I. Water Blank Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

Typical Column Blank using TEVA resin Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

Typical Sample Spectrum 4M HNO3 Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

Direct Injection of Sample into ICPMS Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

99Tc and 187Re Elution Curve from TEVA resin 4 Molar HNO3 Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

99Tc and 187Re Elution Curve from TEVA resin 6 Molar HNO3 Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

99Tc and 187Re Recovery from TEVA resin 6 Molar HNO3 Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

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. Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

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). Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

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 Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

CEM Micro Digestion Vessels 3 ml and 7 ml Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

Conclusion The use of Rhenium coupled with ICPMS analysis offers an excellent alternative for the analysis of 99Tc in waste samples. Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC

Conclusion(II) Beware of strangers bearing gifts, especially if they are from another department. Saturday, November 24, 2018Saturday, November 24, 2018 BWXT Y-12 LLC