Page A European Perspective on the Use of Eichrom Resins Dr Jon Martin BNFL

Page Hunterston A Berkeley Oldbury Dungeness A Littlebrook Chapelcross Calder Hall Wylfa Sizewell A Bradwell Trawsfynydd Hinkley Point A Maentwrog Sellafield Risley HQ BNFL UK Sites

Page An Overview ( ) Background Initial use in emergency response planning. Application to simple matrices. A difficult problem - resolved with Ln.Resin. Application to environmental matrices. Accreditation for plant-support methods. The broader picture.

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Page Environment Magnox AGR Liquid & Gaseous Effluent Waste Characterisation Lab. Decommissioning Lab. Low Level Waste Intermediate Level Waste Central Radiochemical Laboratory CRL Lab Overview

Page Extraction Chromatography - Application to Emergency Methods “The aftermath of an accident is not a time to begin the development of novel procedures”. N. Green, NRPB EEC Intervention Levels: MaterialLimiting Activity Concentration Sr-89/Sr-90Pu-239, Am- 241, Cm-242/4 Others with t 1/2 >10 days (excl. H-3 / C-14 Dairy produce & liquid foods (Bq/kg) Solid & Liquid Foods (Bq/kg)

Page Sequential Emergency Procedure Add radionuclide spikes Microwave digest Anion exchange column Electrodeposit or coppt Pu Sr, Am, Cm not retained Sr.Resin Sr-89/90 determination Am, Cm fraction to TRU.Resin Coppt Am / Cm source

Page Rapid Sr-89 / 90 Procedure Elute from Sr.Resin in 8ml water Cerenkov count (15min) Sr-85 yield determination Add Ultima Gold XR Calculation of Sr-89 & Sr-90 - Correction for Y-90 Liquid scint. count

Page Limitations Sample size. Large excess of Am-241 over Am-243 yield tracer. Uranium breakthrough in Pu spectrum. Batch size dominated by microwave digestion. Sampling uncertainty. Merits <24 hour turnaround, incl. Screening of 80 samples & analysis of 6. Addresses required limits of detection and accuracy. Introduced the benefits of extraction chromatography…

Page Summary of routine methodology…1 AnalysisClassical separationExtraction chromatography Comments TritiumDistillationTritium.Resin investigated but clean-up not sufficient for Magnox effluent. C-14Wet / dry oxidation S-35Wet oxidation and chemical isolation and / or cation exchange C1-36Chemical isolation Ca-45Chemical isolationSr.Resin + classical chemistry RE.Resin investigated but little Mn-54 clean-up Mn-54Chemical isolation Fe-55Solvent extraction Ni-63Ni.Resin

Page Summary of routine methodology…2 AnalysisClassical separation Extraction chromatography Comments Sr-90 / Sr- 89 Sr.ResinExcepting large volume milk samples Tc-99 TEVA.ResinLow requirement I-129 Solvent extractionABEC.ResinExtraction chromatography not normally necessary Pm-147 Sm-151 Ln.Resin Pb-210 Sr.Resin Po-210 Distillation or direct auto deposition Sr.Resin Ra-226 Uranium / Thorium U/TEVA.Resin / TEVA Resin TransuranicsTEVA / TRU. Resins

Page Pm-147 High abundance in fresh fission product mixtures. Sm-151 Increasing importance in decayed fission product mixtures. Pm-147 / Sm-151 Analysis...Why? Pure soft  -active radionuclides. Radiotoxicity comparable to that of carbon-14. No suitable isotopic yield tracer. No naturally occuring isotope. No suitable isotopic yield tracer. Gravimetric yield determination possible. What yield tracer?

Page Assessment of ‘Low Abundance’ Isotopes' compliance with de minimis Criteria for Disposal RadionuclideMaximumTheorectical Activity per Consignment de minimis Se Y Zr Nb-93m Tc Pd Sn I Cs Sm

Page CePrNdPmSmEuGdTbHoDyTmErYbLu Ho-166m [1200y,  ] Eu-154 [8.59y,  580 keV] Eu-155 [4.85y,  160 keV] Sm-151 [88.7y,  76 keV] Pm-147 [2.6y,  225 keV] Pr-144 [285d,  keV] Ce-144 [285d,  318 keV] Abundance rel. to Cs-137 5GWd/T, 4 years decayed Pm-147 / Sm-151 Analysis...Interferences

Page CePrNdPmSmEuGdTbHoDyTmErYbLu Natural Samarium...natural  Natural Neodymium...natural  Gd-148,  [3.27 MeV] Pm-147 Analysis...Yield tracers

Page Ln.Resin - not to be confused with RE.Resin (of course!) HDEPH: bis(2-ethylhexyl) phosphoric acid supported on Amberchrom CG-71 at a 40%w/w loading. Original work by Horwitz & Bloomquist, J. Inorg. Nucl. Chem. 17, 425 (1975). Promethium- 147 by Eichrom’s Ln.Resin

Page Am Eu Normalised count rate (Arb) Volume (cm 3 ) Am Pm Gd 0.15 M nitric acid0.25 M nitric acid0.4 M nitric acid Pm-147 / Sm-151 Analysis...Gd-148 yield tracer

Page Normalised count rate / Sm concentration (Arb) Volume (cm 3 ) Pm-147 / Sm-151 Analysis...Natural Sm yield tracer

Page Summary of Pm-147 / Sm – 151 Results Sample description Pm-147 ResultSm-151 ResultRatio FMDT liquid effluent annual bulk (15/06/97) mean of 4 results AETP sludge dissolution liquor – A AETP sludge dissolution liquor – B ILW resin sample (Lewatit DN) LLW QC spiked solution ( )%

Page Benefits Approximate 60% cost reduction per analysis through time savings and larger batches. Fully validated, accredited methods with comprehensive uncertainty budgets. Methods proven at national and international intercomparison exercises.

Page Environmental / Bioassay Matrices - Overcoming the Interferences Sr-90 in fish, urine, faecal ash.  3g Sr.Resin in column. Pu / Am in soils.  Anion exchange pre-clean-up. Preliminary work on pre- concentration of transuranics on Diphonix, followed by Fenton’s Reagent destruction of organics - see work by Bill Burnett, FSU.

Page Application of Eichrom technology to other BNFL processes Support to reprocessing: product quality and accountancy. Tc-99 analysis - TEVA - various matrices. Environmental monitoring programmes. Application of Eichrom technology in Europe Mature processes which are broadly used in a wide range of applications. PROCORAD - laboratories from >20 countries. Many used Eichrom extractants.