Foundations ofExtraction Chromatography“Eichrom‐101”
Presented byLawrence Jassin andwww.alarasolutions.com
TerenceO’Brienwww.eichrom.com

Eichrom / NPO• Founded in 1990

– 2008 Eichrom Technologies acquired Nuclear
Power Outfitters– 2009 Eichrom moved entire company into one
facility in Lisle, IL just ~30 miles of downtown
ChicagoWhy Do Sample Preparation

Toomuchliquid
ALPHA
SPECTROMETERS

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Sample Preparation Orientation
Sample Preparation Concepts/ Measurement Equipment Choice
Extraction Chromatography (EXC)
Fundamentals
EXC Resin Characterization and Comparisons
Importance of Filter MediaRare Earth‐Micro Co‐Precipitationwww.eichrom.com

Your goals for Sample Preparation
Minimize sample prep time and waste generation
Trade offs between– sample size, detection level, sample preparation rigor

Data quality objectives
Detection instrument selection
Instrument's capabilities

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Detection Instrument forRadionuclide Measurements
Measurement of gamma energy– Good spectral resolution, minimal sample prep

Measurement of beta energy– Minimal spectral resolution, requires separation ofother beta and alpha emitters and chemical effects

Measurement of alpha energy– Some spectral resolution, sample prep used toeliminate spectral and general mass interferences
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Measurement of Gamma Energy

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Radiologic Screening Counters
Gas‐Flow Proportional Counters– Alpha/Beta Weight Attenuation– Alpha/Beta Cross Talk Calibration– Alpha/Beta Isotope Calibrationwww.eichrom.com

Liquid Scintillation Counterswww.eichrom.com

Measurement of Beta Energy

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Measurement of Alpha Energy

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Americium Spectrum after TRU Resin Separation
presence of rare earths degrades spectrum‐ self absorption issues

Am‐241

Am‐243www.eichrom.com

Am Spectrum after TEVA Resin Separation
Lanthanide elements removed ‐ cleaner spectrum

Am‐241

Am‐243www.eichrom.com

Actinides by ICP-MS:
The issues
Polyatomic ions230ThH and 231Pa
236UH and 237Np
237NpH and 238U
238UH and 239Pu
240PuH and 241Am
242PuH and 243Am

Isobars
236U and 236Np
238U and 238Pu
241Pu and 241Am
242Pu and 242Am

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Sample Preparation Steps
Sample Modification– Digestion– Leach– Fusion

Volume Reduction– Precipitation– Evaporation– Ion Exchange

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Solvent Extraction

EM1+n, M2+n

OrganicPhaseM1•E+nAqueousPhaseM2+nwww.eichrom.com

Extraction Chromatography

Solvent Extraction

Column Chromatography

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Extraction Chromatographic Resin

Inert support =Macroporous Acrylic Resin

Example Stationary Phases•Crown Ether (Sr)
•CMPO (TRU)•DAAP (UTEVA)
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Metal Anion Complex Formationwww.eichrom.com

ResinCharacterization

Extraction Chromatography Principles

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• Smaller
particles,
sharper
elutionbands• Peakmaximum
corresponds
to k’What is k’k’ is the number of free column volumes to the peakconcentration maximum of the analyte of interest
A free column volume is related to bed volume by a factorof 0.65
For a 2 mL resin bed volume, the free column volume is
1.3 mLk’ is approximately equal to Dw divided by 1.9
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Factors that Control
Target Analyte Retention
1. Elements with similar k’ tend to compete
2. High concentrations of competing elements
3. Acid type and concentration(Nitric, HCl, Sulfuric)
4. Complexants added to the sample or found in
the sample (Oxalic, Phosphoric, HF)
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Choose the appropriate
amount of resinwww.eichrom.com

And Size of Resin:
A‐Grade for Gravity Flow
S‐Grade with Vacuum
F‐Grade for Separationsof elements with very
similar k’

F‐grade 25‐53µ80x
S‐grade 50‐100µA‐grade 100‐150µ80x80x

Add InSung or SOWA siteswww.eichrom.com

EXC Resin Extractant Choice
Ionic Recognition Extractant based resin– Analyte retention related to charge and ionic radii

Neutral and Anionic Extractant based resin– Analytes are directly hydrogen ion dependant, althoughanionic extractant based resins tend to show reduced
analyte uptake as the acid competes

Acidic Extractant based resin– Analyte retention is inverse hydrogen ion dependant
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Sr Resin / Ionic Recognition
di‐t‐butylcyclohexano 18‐crown‐6
Sr+2, Pb+2

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Elution ofCommon Elements
AndFission Products
On Sr ResinAnionic Extractant
TEVA Resinwww.eichrom.com

TRU Resin

CMPO/TBP
NeutralExtractant

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TRU Resinwww.eichrom.com

TRU Resin: Neutral Extractant
DGA Resin: Neutral extractant/ ionic recognitionO
C8H17POON

C8H17 NOON

C8H17
C8H17

C8H17

DGATRU

Am3+ + 3X‐ + 3E ↔ AmX3E3
X = Cl‐ or NO3‐www.eichrom.com

Actinides on TRU vs. DGA
out of HNO3
DGA Resin, Normal

TRU Resin

610Pu

510Th

410Pu

U
310k'ThAm

210Am

110UPu(IV)
Th(IV)U(VI)
Am(III)

010-110-210-1

100

10[HNO3]

1-2

10 10-1

100

10[HNO3]

110www.eichrom.com

Actinides on TRU vs DGA
out of HCl
TRU Resin

DGA Resin, Normal

610Pu(IV)Th(IV)U(VI)
Am(III)

510Pu

410Pu
310k'210UTh

1100Th10UAmAm-110-210-110010[HCl]1-210 10-110010[HCl]110

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DGA Resin
Very high k’ for trivalent lanthanides and actinides
No uptake of Fe(III) from nitric acid‐Improvement
over TRU Resin for Am work
Separation of Cm‐242 and Cm‐244 from Ac‐225 andFr‐221‐Single aliquot
Retention of Y for Rapid Sr‐89 Sr‐90 determinations
Fe‐55/Eu‐154‐High Level Nuclear Waste
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UTEVA Resin(DAAP)
Diamyl Amylphosphonate
Neutral Extractant

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The LN Series of ResinsOOPPOHDEHP (LN)

OO

OHOH

AcidicExtractants

HEH[EHP] (LN2)OPOH

H[TMPeP] (LN3)

M3+ + 3(HY)2 ↔ M(HY2)3 + 3H+

Ln Resin
Acid Dependencyk’ for Ln Resinin HNO3

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Rare Earth Co-Precipitation for
Actinide Sample Alpha Source
Starting Sample

Add Rare Earth
Carrier (La, Ce, or Nd)

Add Conc. HF acid

Wait ~30 minutes

Filter through0.1µ Resolve Filter

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Mountand CountQuality Control for Alpha Spec

Gravity Flow vs. Vacuum Assistedwww.eichrom.com

PTFE Laminate Alpha Air
Monitoring Filters• Quality Control Specification:– Background < MDA for α & β– Resolution verified <60 KeV FWHM
– Minimal curling <4.0 mm deflection• The filters have a easy to determineorientation:“Grid side down, Opposite Air flow”

Eichrom’s Resolve PTFE Laminate
Filters®

• Volumetric Flow

– Resolve 47mm PTFE Filters have maintained aDOP 99.99% efficiency testing rating up to9 CFM = 254 LPM– PTFE Filters maintain integrity even withmg of material loaded on the filter for your harshest
applications.

eichrom

Health Physics
Sampling Smears
Swipe/Smears forcontamination
monitoring.
Two Formats:•Paper Backed withrecorder paper•Bulk Packaged

Features of Swipe / Smears• 44.4mm (1 ¾ inch) in Diameter Cloth Smear• Pressure Sensitive adhesive backing/support– Allows for easy reattachment to support or planchet• Backing and Smear can beremoved together from supportfor analysis

Conclusion
1990: Eichrom was founded to improve theefficiency of radiochemical separations
through the commercialization of extraction
chromatography
2012: Today, Eichrom supports a global
customer base with a portfolio of extraction
chromatographic resins, methods and anextensive bibliography of proven results.
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