Page 16747 A European Perspective on the Use of Eichrom Resins Dr Jon Martin BNFL.
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Page 1 6747 A European Perspective on the Use of Eichrom Resins Dr Jon Martin BNFL
Transcript of Page 16747 A European Perspective on the Use of Eichrom Resins Dr Jon Martin BNFL.
Page 16747
A European Perspective on theUse of Eichrom Resins
Dr Jon Martin
BNFL
Page 26747
Hunterston A
BerkeleyOldbury
Dungeness A
Littlebrook
Chapelcross
Calder Hall
Wylfa
Sizewell ABradwell
Trawsfynydd
Hinkley Point A
Maentwrog
Sellafield
Risley HQ
BNFL UK Sites
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An Overview (1992-1998)
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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Environment
MagnoxAGR
Liquid & GaseousEffluent
WasteCharacterisationLab.
DecommissioningLab.
Low Level Waste
IntermediateLevel Waste
CentralRadiochemical
Laboratory
CRL Lab Overview
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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:
Material Limiting Activity ConcentrationSr-89/Sr-90 Pu-239, Am-
241, Cm-242/4Others with t1/2 >10
days(excl. H-3 / C-14
Dairy produce &liquid foods (Bq/kg)
125 20 1000
Solid & LiquidFoods (Bq/kg)
750 80 1250
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Sequential Emergency Procedure
Add radionuclidespikes
Microwave digest
Anion exchangecolumn
Electrodeposit orcoppt Pu
Sr , Am, Cm notretained
Sr .Resin
Sr -89/90determination
Am, Cm fraction toTRU.Resin
Coppt Am / Cmsource
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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
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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…
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Summary of routinemethodology…1
Analysis Classical separation Extractionchromatography
Comments
Tritium Distillation Tritium.Resin investigated butclean-up not sufficient for Magnoxeffluent.
C-14 Wet / dry oxidation
S-35 Wet oxidation andchemical isolation and /or cation exchange
C1-36 Chemical isolation
Ca-45 Chemical isolation Sr.Resin + classicalchemistry
RE.Resin investigatedbut little Mn-54 clean-up
Mn-54 Chemical isolation
Fe-55 Solvent extraction
Ni-63 Ni.Resin
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Summary of routinemethodology…2
Analysis Classicalseparation
Extractionchromatography
Comments
Sr-90 / Sr-89
Sr.Resin Excepting large volume milksamples
Tc-99 TEVA.Resin Low requirement
I-129 Solvent extraction ABEC.Resin Extraction chromatography notnormally necessary
Pm-147Sm-151
Ln.Resin
Pb-210 Sr.Resin
Po-210 Distillation or directauto deposition
Sr.Resin
Ra-226
Uranium /Thorium
U/TEVA.Resin /TEVA Resin
Transuranics TEVA / TRU.Resins
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Pm-147 High abundance in fresh fission
product mixtures.
Sm-151Increasing importance in decayed
fission product mixtures.
Pm-147 / Sm-151Analysis...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?
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Assessment of ‘Low Abundance’ Isotopes' compliance with de minimis Criteria for Disposal
Radionuclide Maximum TheorecticalActivity per Consignment
de minimis
Se-79 0.0075 13Y-91 10300 13Zr-93 0.0047 13Nb-93m 0.029 13Tc-99 0.37 13Pd-107 0.002 13Sn-126 0.28 13I-129 0.00069 0.05Cs-135 0.019 13Sm-151 6.3 13
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Ce Pr Nd Pm Sm Eu Gd Tb HoDy TmEr Yb Lu
Ho-166m [1200y, ]
Eu-154 [8.59y, 580 keV]........1.9
Eu-155 [4.85y, 160 keV]........2.6
Sm-151 [88.7y, 76 keV].....................0.31
Pm-147 [2.6y, 225 keV].............................79
Pr-144 [285d, 2.996 keV]
Ce-144 [285d, 318 keV]..........................................................23
Ab
un
dan
ce r
el. t
o C
s-13
7 (%
)@
5G
Wd
/T, 4
yea
rs d
ecay
ed
Pm-147 / Sm-151Analysis...Interferences
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Ce Pr Nd Pm Sm Eu Gd Tb HoDy TmEr Yb Lu
Natural Samarium...natural
Natural Neodymium...natural
Gd-148, [3.27 MeV]
Pm-147 Analysis...Yield tracers
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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
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Am
Eu
0 10 20 30 40 50 60 700.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Nor
mal
ised
cou
nt r
ate
(Arb
)
Volume (cm3)
Am
Pm
Gd
0.15 M nitric acid 0.25 M nitric acid 0.4 M nitric acid
Pm-147 / Sm-151Analysis...Gd-148 yield tracer
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0 50 100 150 200 250 3000.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Nor
mal
ised
cou
nt r
ate
/ Sm
con
cent
rati
on (
Arb
)
Volume (cm3)
Pm-147 / Sm-151Analysis...Natural Sm yield tracer
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Summary of Pm-147 / Sm – 151 Results
Sampledescription
Pm-147 Result Sm-151 Result Ratio
FMDT liquid effluentannual bulk (15/06/97)
698 + 49mean of 4 results
9.28 + 2.83 75 + 24
AETP sludgedissolution liquor – A
2.40 + 0.20 1.92 + 0.22 1.25 + 0.18
AETP sludgedissolution liquor – B
1.35 + 0.15 0.949 + 0.099 1.42 + 0.22
ILW resin sample(Lewatit DN)
18.3 + 1.4 13.0 + 1.0 1.41 + 0.15
LLW QC spikedsolution
(-2.8 + 10.8)%
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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.
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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.
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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 EuropeMature processes which are broadly used in a wide range of applications.PROCORAD - laboratories from >20 countries. Many used Eichrom extractants.
