1. On-line Actinide Quantification with Extractive Scintillating Resins Timothy A. DeVol, James E. Roane, Lara D. Hughes Clemson University Eichrom Users’ Group Workshop May 4, 2004

2. Need for Monitoring Method Radionuclide contamination in natural waters – natural – anthropogenic Radionuclide specific and gross alpha analyses – primarily laboratory based – can be time intensive and costly Need for in-situ and on-line monitoring – site assessment before, during and following remedial action

3. Sample Prep Concentration Separation Detection Data Sample Prep Concentration Separation Detection Data Dual Functionality Simultaneous Concentration and Detection Heimbuch, et al., 1964 Li and Schlenoff, 1994 DeVol, et al., 1997 Campi, et al., 1998 Link and Synovec, 1999 Egorov, et al., 1999 Headrick, et al., 2000

4. Extractive Scintillating Resin Inert polystyrene chromatographic supports (100 - 150  m particle size, ~700 m 2 /g)

5. Experimental- Flow cell procedure Flow cell –resin dry packed into FEP Teflon tubing –placed in front of PMT(s) Test procedure –conditioning, loading and washing steps with appropriate reagents –collecting on-line data during flow –pulse height spectra before and after load –aliquots of effluent analyzed off-line (mass balance) Radioactivity –spiked solutions of 241 Am, 239 Pu and 233 U –Anthropogenic samples –natural groundwater containing U

6. Extractive Scintillator in Flow-cell Radiation Detector Computer Effluent Sample Loading Solution Eluant LSC Simultaneous Separation and Detection Manually controlled pump

7. Flow-Cell Detection Systems Ultraviolet Illumination Coincidence System for TRU ES Modified Hidex Triathler for Actinide ES Modified Eberline E-600 for Tc ES II

8. TRU ES Loading Profile I IIIII I Condition w/ 2 M HNO 3 II Load 239 Pu in 2 M HNO 3 III Rinse w/ 2 M HNO 3

9. TRU ES Pulse Height Spectra 239 Pu Background

10. Chromatographic capacity of the ES TRU resin as illustrated by the loading and elution of 233 U k’ ~ 3000

11. Sequential Elution of 241 Am, 239 Pu and 233 U from TRU ES Resin Off-Line Counting On-Line Counting

12. Analysis of SRTC High Level Waste Sludge Plot of average activity (n=3) with 1 standard deviation

13. On-Line Monitoring 233 U in Synthetic Groundwater CR(cps) = 0.151 + 0.650*V(L) R= 0.95 CR(cps) = 0.165 + 4.631*V(L) R= 0.99 CR(cps) = 0.159 + 2.729*V(L) R= 0.97 8.62 Bq L -1 4.92 Bq L -1 1.74 Bq L -1

14. Monitoring Natural Uranium in Water Expected 7.48 Bq/L Measured 9.6 Bq/L from slope of first 50 mL 125 mL sample acidified to 0.5 M HCl

15. Actinide ES Resin 685  g U/L 17.4 Bq/L

16. Actinide ES Resin  30  g uranium/L (0.76 Bq/L) Natural Uranium in Groundwater acidified to pH 1

17. Summary of Results

18. Conclusions Extractive scintillating resins are selective dual- purpose media –High   –Transparent to scintillation light Chromatographic property of ES resin is similar to non-scintillating commercially available resin Quantification has been demonstrated on-line Applicable toward environmental screening applications. Continuing to work on solving the stability, sensitivity, benign sample matrix, and reusability issues

19. FUTURE WORK Solve the problems that affect the results, such as, –Chemical luminescence –Dark adaptation time –Signal variation with radionuclide position in flow-cell Optimize flow-cell geometry for maximum sensitivity Develop ruggedize field instrument and demonstrate in the field Off-line evaluation procedures

20. Acknowledgments Dr. James Harvey, Dr. Jonathon Duffey, and Joel Williamson at Eichrom Technologies, Inc. NSF SBIR Phase I contract # NSF/SBIR-9760934 DOE Office of Science (BER) grant DE-FG07-99ER62888