Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides
description
Transcript of Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides
![Page 1: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/1.jpg)
Chromatographic Separation and Measurement of Charged-Particle Emitting
Radionuclides
Timothy A. DeVol, Ph.D., C.H.P.
Environmental Engineering and Science
Clemson University
16 May 2000
![Page 2: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/2.jpg)
Introduction to Dual Functionality Materials
• Liquid Extractive Scintillators– Ludwick, Health Physics, 1961, 6, 63-65.– McDowell and McDowell, Liquid Scintillation Alpha Spectrometry, CRC
Press, Boca Raton, 1994.
• Scintillating Cation and Anion Ion Exchange Resin– Heimbuch, et al., Radioisotope Sample Measurement Techniques in Medicine
and Biology, Proceedings of the International Atomic Energy Agency Symposium, Vienna, May 24-28, 1965.
• Solid Extractive Scintillators for 90Sr and 99Tc– Egorov et al., Anal. Chem 71 (1999) 5420-5429
• Solid Extractive Scintillators for 90Sr, 99Tc and Actinides – DeVol et al., Radioactivity&Radiochemistry Vol. 11 #1 (2000)
![Page 3: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/3.jpg)
Separation and Detection Schemes
• Single scintillation crystal, e.g. CaF2:Eu, anthracene
• Extractant coated onto inert scintillator
• Mixture of extraction resin with granular scintillator
• Extractant impregnated into a scintillating chromatographic resin (ScintEx)
![Page 4: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/4.jpg)
Solid Extractive Scintillators
• Sequential Extraction Chromatography and Flow-cell Detection
Off-line quantification
• Simultaneous Extraction Chromatography and Flow-cell Detection
On-line quantification
![Page 5: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/5.jpg)
Materials and Methods
• Mixed-ResinMixture of:– 100 - 150 m TEVA Resin or Sr Resin
– 100 - 200 m BC-400 Plastic Scintillation Beads (Bicron)or 63 - 90 m GS-20 Scintillating Glass (Applied Scintillation Technology)
![Page 6: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/6.jpg)
Extractive Scintillator Resin
• ScintEx resin (Patent Pending)– Inert polystyrene chromatographic resin (Amberchrom CG-
161c) impregnated with PPO and DM-POPOP using a modification of the Ross 1991 procedure
– Scintillating chromatographic bead impregnated with extractant (Eichrom proprietary technology)
• Extractant for Sr• ABEC-2000• Quaternary Amine, Aliquat-336 (TEVA)
• CMPO extractant in TBP for actinides
![Page 7: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/7.jpg)
Off-Line Evaluation Procedures
• Resin dry packed into 9 mm x 50 mm opaque column
• Conditioning, loading and wash performed with standard Eichrom procedures
• Column placed in 7-mL HDPE vial WITHOUT introduction of LSC cocktail
• Activity quantified with Hidex Triathler liquid scintillator counter
![Page 8: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/8.jpg)
Hidex Triathler
![Page 9: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/9.jpg)
Results and Discussion
• Mini-Column Experiments (Off-Line)– Compare pulse-height spectra (luminosity) and
detection efficiency
• Flow-Cell Experiments (On-Line)– Loading and elution profiles (loading and
detection efficiency, and total recovery)– Regeneration capability
![Page 10: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/10.jpg)
89Sr Pulse-Height Spectra from Triathler
0.1
1
10
10 100 1000
Channel Number
Net Count Rate (cps)
Sr ScintEx O; 50.8%Sr GS20M; 50.3%Sr BC400M; 81%SrGS20; 14.4%Sr ScintEx; 9.1%
![Page 11: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/11.jpg)
Triathler Pulse-Height Spectra for 89Sr and 90Sr on Sr ScintEx O
0.1
1
10
10 100 1000
Channel Number
Net Count Rate (cps)
Sr-89, 50.8%Sr90/Y90, 36.0%Sr-90, 14.4%
![Page 12: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/12.jpg)
Schematic of On-Line Flow-Cell Detection System
Computer
Effluent
Sam
ple
Loa
ding
Solu
tion
Elu
ant
LSC
Radiation Detector
PMT PMT
Flow-cell
Manually controlled pump
![Page 13: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/13.jpg)
Flow-Cell Radiation Detection System
IN/US -Ram Model 1
![Page 14: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/14.jpg)
Extractive Scintillator Flow-Cell
Extractive scintillator flow-cellwas constructed of with <0.5 gof resin packed into 1.5 mm IDx 140 mm polytetrafluoro-ethylene tubing to yield an approximate pore volume of 200-400 L. The tubing is coiled to an approximate diameter of 2.54 cm and placed between the photomultiplier tubes of the radiation detector.
![Page 15: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/15.jpg)
Loading and Elution of 99Tc(VII)TEVA/BC-400 Mixed Resin
10-1
100
101
0
0.2
0.4
0.6
0.8
1
0 500 1000 1500 2000 2500 3000 3500 4000
99Tc in 2-M HCl
2-M HCl
8-M HCl
Count Rate (cps)
Flow Rate (mL min
-1)
Time (s)
99Tc) = 7.5%
![Page 16: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/16.jpg)
Loading and Elution of 99TcTEVA/BC-400 Mixed-Resin Flow-Cell
137Cs Interference Test
10-1
100
101
102
103
0 1000 2000 3000 4000 5000 6000
Count Rate (cps)
Time (s)
99Tc in 2 M HCl
2 M HCl
8 M HNO3
137Cs in 2 M HCl
99Tc; 5 mL; 24 Bq mL-1
137Cs; 1 mL; 7.2 kBq mL-1
![Page 17: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/17.jpg)
Loading and Elution of 99TcABEC ScintEx Flow-Cell
0
200
400
600
800
1000
1200
0 500 1000 1500 2000 2500 3000 3500 4000
Counts per 10 s
Time (s)
Loading Efficiency ~ 100%Total Tc Recovery ~ 99.5%Detection Efficiency ~ 79%
99Tc in 4M NaOH
4 M NaOH
DDI H2O
![Page 18: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/18.jpg)
Loading and Elution of 99TcTEVA ScintEx Flow-Cell
0
200
400
600
800
1000
0 1000 2000 3000 4000
Counts per 10 s
Time (s)
Loading Efficiency = 99.9%Total Tc Recovery = 99.4%Detection Efficiency = 51%
99Tc in 0.1 M HNO3
0.1 M HNO3
8 M HNO3
![Page 19: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/19.jpg)
Loading and Regeneration of TEVA ScintEx
0
20
40
60
80
100
0
20
40
60
80
100
1 2 3 4 5 6 7 8 9 10 11
Detection Efficiency - 0.1 M HNO3
Detection Efficiency - 2 M HNO3
Loading Efficiency
Total Recovery
Detection Efficiency (%)
Loading Efficiency or Total Recovery (%)
Trial #
![Page 20: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/20.jpg)
89Sr Loading and Elution Profile on Sr ScintEx O
(89Sr) = 65.4%
![Page 21: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/21.jpg)
Loading 90Sr/90Y on Sr ScintEx P
0
2
4
6
8
10
12
14
16
18
0 500 1000 1500 2000 2500 3000
Time (s)
Count Rate (cps)
Sr/Y-90, 92.5 Bq
Y-90, 160 Bq
Sr)= 40%
102
![Page 22: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/22.jpg)
Multiple Loading and Elution of 89Sr on Sr ScintEx O
0
20
40
60
80
100
120
0 5000 10000 15000
Time (s)
Count Rate (cps)
Avg. Detection efficiency 60 4%
Avg. Loading efficiency 101 ± 1%
65.4%58.8% 57.6% 59.6%
![Page 23: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/23.jpg)
TRU ScintEx ResinPulse Height Spectrum
![Page 24: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/24.jpg)
Sequential Elution of 241Am, 239Pu and 233U from TRU ScintEx Resin
Off-Line Counting
On-Line Counting
Sample Load in 2-M HNO3
4-M HCl
4-M HCl + 0.02-M TiCl32-M HCl0.1-M Ammonium Bioxalate
![Page 25: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/25.jpg)
Conclusions
• Extractive scintillator media can be realized a number of ways• Extractive scintillator media can be selective to analyte of interest
– demonstrated with technetium-selective, strontium-selective and actinide-selective extractant
• Loading, retention, and elution similar to non-scintillating resin• Quantification has been demonstrated on-line and off-line• Limited spectroscopy appears to be available with the actinide-
selective ScintEx resin• Absolute detection efficiency ranges from ~40% for 90Sr to near
100% for actinide- selective ScintEx resin
![Page 26: Chromatographic Separation and Measurement of Charged-Particle Emitting Radionuclides](https://reader036.fdocuments.us/reader036/viewer/2022062518/56814575550346895db2462c/html5/thumbnails/26.jpg)
Acknowledgments
• James Harvey, Eichrom IndustriesJonathan Duffey, formerly from Eichrom
• From Clemson University:Robert Fjeld, Alena Paulenova (on leave from Comenius´ University, Slovak Republic), James Roane
• John Leyba, WSRTC• NSF SBIR Phase I contract # NSF/SBIR-9760934• South Carolina University Education and Research Foundation
TOA #KC86372-O.• DOE Environmental Management and Science Program, Project
#70179