Eichrom Technologies社のGeneral Review

Foundations of
Extraction Chromatography
“Eichrom‐101”
Presented by Lawrence Jassin and www.alarasolutions.com
Terence O’Brien
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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
Too
much
liquid
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 Media
Rare Earth‐Micro Co‐Precipitation
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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 for
Radionuclide Measurements
Measurement of gamma energy
– Good spectral resolution, minimal sample prep
Measurement of beta energy
– Minimal spectral resolution, requires separation of other beta and alpha emitters and chemical effects
Measurement of alpha energy
– Some spectral resolution, sample prep used to eliminate 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 Calibration
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Liquid Scintillation Counters
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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‐243
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Am Spectrum after TEVA Resin Separation
Lanthanide elements removed ‐ cleaner spectrum
Am‐241
Am‐243
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Actinides by ICP-MS:
The issues
Polyatomic ions
230ThH 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
E
M1+n, M2+n
Organic
Phase
Aqueous
Phase
M1•E+n
M2+n
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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 Formation
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Resin Characterization
Extraction Chromatography Principles
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• Smaller
particles,
sharper
elution
bands
• Peak
maximum
corresponds
to k’
What is k’
k’ is the number of free column volumes to the peak concentration maximum of the analyte of interest
A free column volume is related to bed volume by a factor of 0.65
For a 2 mL resin bed volume, the free column volume is 1.3 mL k’ 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 resin
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And Size of Resin:
A‐Grade for Gravity Flow
S‐Grade with Vacuum
F‐Grade for Separations of elements with very similar k’
F‐grade 25‐53µ 80x
S‐grade 50‐100µ A‐grade 100‐150µ 80x
80x
Add InSung or SOWA sites
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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, although anionic 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 of
Common Elements
And Fission Products
On Sr Resin
Anionic Extractant
TEVA Resin
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TRU Resin
CMPO/TBP
Neutral Extractant
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TRU Resin
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TRU Resin: Neutral Extractant
DGA Resin: Neutral extractant/ ionic recognition
O
C8H17
P
O
O
N
C8H17 N
O
O
N
C8H17
C8H17
C8H17
DGA
TRU
Am3+ + 3X‐ + 3E ↔ AmX3E3
X = Cl‐ or NO3‐
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Actinides on TRU vs. DGA
out of HNO3
DGA Resin, Normal
TRU Resin
6
10
Pu
5
10
Th
4
10
Pu
U
3
10
k'
Th
Am
2
10
Am
1
10
U
Pu(IV)
Th(IV)
U(VI)
Am(III)
0
10
-1
10
-2
10
-1
10
0
10
[HNO3]
1
-2
10 10
-1
10
0
10
[HNO3]
1
10
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Actinides on TRU vs DGA
out of HCl
TRU Resin
DGA Resin, Normal
6
10
Pu(IV)
Th(IV)
U(VI)
Am(III)
5
10
Pu
4
10
Pu
3
10
k'
2
10
U
Th
1
10
0
Th
10
U
Am
Am
-1
10
-2
10
-1
10
0
10
[HCl]
1
-2
10 10
-1
10
0
10
[HCl]
1
10
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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 and Fr‐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 Resins
O
O
P
P
O
HDEHP (LN)
O
O
OH
OH
Acidic Extractants
HEH[EHP] (LN2)
O
P
OH
H[TMPeP] (LN3)
M3+ + 3(HY)2 ↔ M(HY2)3 + 3H+
Ln Resin
Acid Dependency
k’ for Ln Resin
in 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 through 0.1µ Resolve Filter
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Mount and Count
Quality Control for Alpha Spec
Gravity Flow vs. Vacuum Assisted
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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 determine
orientation:
“Grid side down, Opposite Air flow”
Eichrom’s Resolve PTFE Laminate
Filters
®
• Volumetric Flow
– Resolve 47mm PTFE Filters have maintained a
DOP 99.99% efficiency testing rating up to
9 CFM = 254 LPM
– PTFE Filters maintain integrity even with
mg of material loaded on the filter for your harshest
applications.
eichrom
Health Physics
Sampling Smears
Swipe/Smears for
contamination
monitoring.
Two Formats:
•Paper Backed with
recorder 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 be
removed together from support
for analysis
Conclusion
1990: Eichrom was founded to improve the efficiency 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 an extensive bibliography of proven results. www.eichrom.com