Transcript Eichrom’s LN Series of Resins: Characterization and Novel

eichrom
New QC Procedure for Eichrom Resins:
Why We’re Changing
Joel Williamson, Jill Bernstein,
Dan McAlister and Phil Horwitz
Eichrom Technologies, Inc.
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Since the formation of Eichrom, an essential
feature of our quality control system was the
measurement of Dw for each batch of new
resin manufactured.
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Dw was measured under conditions in which the
analyte is strongly retained by the resin and
weakly retained by the resin.
What do these types of measurements tell you?
1.Did you use the correct extractant?
2.Did you use the correct quantity of extractant?
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What Dw does not tell you.
• How completely will an analyte be retained by the
column? In other words, how much breakthrough will
occur?
• When exactly will an analyte elute from the column?
• How efficiently will an analyte elute from the
column? (% recovery)
• How much cross contamination will occur between
two or more analytes?
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New QC Protocols
1) Extractants (Solvent extraction test)
-helps to determine purity of extractant
2) Every batch of resin (Dw Test)
-ensures correct extractant used
3) Resin with new lot of at least one starting material
(New column QC)
a) 1 chromatogram
b) 4 vacuum box tests
-ensures good performance of resin in most
commonly used application
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Chromatogram
Simplified version of common
Eichrom method performed
1. Load
3. Strip
Aliquots taken for gamma, LSC or
ICP-AES analysis
cpm or ppm plotted vs Bed Volumes
Am
Pu
cpm
2. Rinse
Bed Volumes
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Chromatogram
Am
Pu
Important Parameters
cpm
1) Recovery of analytes (>95%)
2) Cross-contamination (<1-3%)
3) Reproducibility (4-5 replicates)
Bed Volumes
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Vacuum Box Test
Essentially the same as the chromatogram test, however, fewer
fractions are collected
Provides reproducibility data
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General Time Line
1) Determine separation schemes to test each Eichrom resin.
2) Perform liquid-liquid extraction (extractants) and chromatogram
and vacuum box tests on quality control retains (10-12 resin lots) to
determine reasonable recovery/separation metrics for future lots.
Cation
Anion
MnO2
Nickle
Tritium
Ln (a+s)
Pb Resin
Beryllium
DGA, br
DGA, n
Sr Resin
UTEVA
TEVA
TRU
3) Implement new QC procedure and provide improved certificates of
analysis for each lot of Eichrom resin.
1)
Progress as
of 4-22-05 2)
3)
Goal: Complete 4 main resins by
summer 2005
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Proposed QC Protocols
TRU: Load: Am and Pu from 3 M HNO3
Rinse: 3 M HNO3 + 0.1 M NaNO2
Strip Am with 4 M HCl
Strip Pu with 0.03 M ammonium oxalate
TEVA: Load: Th and Pu from 3 M HNO3 + 0.1 M NaNO2
Rinse: 3 M HNO3 + 0.1 M NaNO2
Strip Th with 6 M HCl
Strip Pu with 0.02 M HCl + 0.02 M HF
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Proposed QC Protocols
UTEVA: Load: Th and U from 4 M HNO3
Rinse: 4 M HNO3
Strip Th with 6 M HCl
Strip U with 0.1 HCl
Sr:
Load: Sr and Ba from 8 M HNO3
Rinse: 8 M HNO3
Strip Sr with 0.05 M HNO3
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Results (TRU)
cpm/mL vs bed volumes eluate on TRU Resin
o
2 mL cartridge, 100-150 m, 2 mL/min flow rate, 22(1) C
6
10
Load 10.0 mL 3.0 M HNO3 spiked
with
5
10
241
Am or
239
Pu
Rinse
3.0 M
HNO3
+
0.1 M
NaNO2
4
cpm/mL
10
3
10
241
Am
Strip
4.0 M
HCl
239
Pu
Strip
0.03 M
ammonium
oxalate
2
10
Background
1
10
0
10
lot TRA07164
-1
10
0
2
4
6
8
10
12
Bed Volumes
14
16
18
20
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Results (TRU)
Summary of Column QC of 2.0 mL TRU dry-packed cartridgesa
% in
Lot
TRA04164
TRA04224
TRA04264
TRA07164
TRA11024
TRS01294
TRS01274
TRS05034
TRS08244
TRS11114
TRF06294
a
% in 0.03 M Oxalate
6 BV
5 BV
99.5
0.2
0.4
99.3
0.3
99.4
0.2
99.6
0.6
97.3(9)
0.1(1)
98.0(9)
0.1(1)
98.4(7)
0.1(1)
99.4
0.2
99.1
0.1
99.4
0.3
99.8
0.1
95.0
0.2
95.2
0.1
98.0
0.2
98.3
1.0(4)
97.9(3)
1.3(8)
97.1(7)
0.9(5)
97.0(9)
0.3
98.0
0.2
98.6
0.2
95.5
0.2
98.4
Analyte Load/Rinse
b
Am
0.2
c
Pu
0.2
Am
0.5
Pu
0.1
Am
0.4
Pu
0.1
Am
0.1
Pu
0.3
Am
0.2(2)
Pu
0.1(1)
Am
0.2(1)
Pu
0.1(1)
Am
0.2(2)
Pu
0.1(1)
Am
0.3
Pu
0.0
Am
0.6
Pu
0.0
Am
0.3
Pu
0.1
Am
0.0
Pu
0.0
Load 10 mL 3.0 M HNO3 spiked with
241
% in 4 M HCl
241
Am or
239
#
replicates
4.4
3.8
1.9
3.7
0.3(1)
1.8(2)
0.5(1)
2.7(7)
0.5(1)
2.9(9)
1.9
1.3
4.2
1.4
Pu, Rinse 5 mL 3.0 M HNO3 + 0.1 M NaNO2, Strip
Am with 12 mL
4 M HCl, Strip 239Pu with 0.03 M ammonium oxalate
b
column
activityd
Determined by gamma counting
1
1
>95% yields for Pu
and Am
Good separation of Pu
and Am
1
1
5
5
<1% Pu in Am
<1.5% Am in Pu
Very reproducible
5
1
1
different lots
same lot
1
1
Only significant
variability observed
was the amount of Pu
remaining on column
c
Determined by liquid scintillation counting
d
% of Pu activity remaining on column following 0.03 M oxalate strip
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Results (TEVA)
cpm/mL vs bed volumes eluate on TEVA Resin
o
2 mL cartridge, 100-150 m, 2 mL/min flow rate, 22(1) C
6
10
Load 10.0 mL 3.0 M HNO3 + 0.1 M NaNO2
spiked with
5
10
230
Th or
Pu
Strip
6.0
M
Rinse 230
Th
HCl
3.0 M
HNO3
4
10
cpm/mL
239
Strip
0.02 M HCl
0.02 M HF
239
Pu
3
10
2
10
Background
1
10
0
10
lot TEA07244
-1
10
0
2
4
6
8
10
12
14
Bed Volumes
16
18
20
22
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Results (TEVA)
Summary of Column QC of 2.0 mL TEVA dry-packed cartridgesa
% in
Lot
TEA10144
TEA10114
TEA07244
TEA07154
Analyte Load/Rinse
Thb
0.6
Pub
1.0
Thb
TEA03254
TES10044
TES11124
TES11204
TEF10254
TEF01274
a
Strip
b
c
98.5
0.4
0.3
91.2
95.7
0.4
5.7
1.0
0.7
94.1
3.1
97.2(9)
1.8(9)
0.1(1)
Pub
1.1(1)
0.3(1)
95.8(7)
2.2(7)
Thb
0.7
97.2
0.2
b
0.8
0.3
90.5
8.6
Th
b
0.5(2)
97.2(9)
2.0(9)
0.1(1)
Pub
1.1(1)
0.2(1)
98.2(1)
0.2(1)
b
0.5
98.6
0.4
Pu
b
0.9
0.4
95.2
2.6
Thb
0.2(1)
97(2)
2.0(9)
0.1(1)
Pub
98.3(1)
0.1(1)
Th
0.2(1)
Th
0.5
98.4
0.6
Pub
0.8
0.3
95.2
b
0.6
98.0
1.1
b
1.0
0.5
93.3
b
0.5
98.4
0.6
Pu
b
0.8
0.3
95.2
3.9
Thb
0.2(1)
94(3)
5(3)
0.1(1)
Pub
0.3(1)
0.1(1)
98.6(1)
0.5(1)
Th
b
0.2(1)
98.6(2)
1.0(1)
0.1(1)
Pub
0.3(1)
0.1(1)
98.8(1)
0.3(1)
Th
Th
Th with 10 mL 6 M HCl, Strip
239
230
Th or
239
3.9
4.9
<1% Pu in Th
<2% Th in Pu
Very reproducible
2
1
1
1
Pu, Rinse 5 mL 3.0 M HNO3,
Pu with 10 mL 0.02 M HCl + 0.02 M HF
3
1
0.9(1)
Good separation of Pu
and Th
3
1
b
>95% yields for Pu
and Th
1
1
1.0(1)
Load 10 mL 3.0 M HNO3 + 0.1 M NaNO2 spiked with
230
+ 0.02 M HF
Thb
Pu
TES11124
1.5
% in 6 M HCl
column
# of
activityc replicates
Pub
Pu
TEA04014
% in 0.02 M HCl
2
2
different lots
same lot
Only significant
variability observed
was the amount of Pu
remaining on column
Determined by liquid scintillation counting
% Pu or Th remaining on column following 0.02 M HCl + 0.02 M HF Strip
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Certificate of Analysis
No. CAXXXXX
Eichrom’s TRU Resin
TRAXXXXX
Product:
Lot #:
Eichrom’s TRU Resin Lot # TRAXXXXX has been manufactured according to Eichrom’s standard
operating procedures. This lot has been tested in accordance with Eichrom’s quality assurance policy and
procedures. This lot of product meets all Eichrom quality specifications.
ANALYSIS RESULTS
Test Value
Specification
Result
Appearance
Distribution Ratio, 3.1 N nitric acid
% 241Am stripped in 4M HCl
% 241Am stripped in 0.03M (COONH4)2
241
Am activity balance
% 239Pu stripped in 0.03M (COONH4)2
% 239Pu stripped in 4M HCl
239
Pu activity balance
Extractant distribution ratio, strip
White beads
 60
TBD
TBD
TBD
TBD
TBD
TBD
TBD
Pass
cpm/mL vs bed volumes eluate on TRU Resin
o
10
2 mL cartridge, 100-150 m, 2 mL/min flow rate, 22(1) C
6
cpm/mL
Load 10.0 mL 3.0 M HNO 3 spiked
10
5
10
4
10
3
10
2
10
1
10
0
with
241
Am or
239
Pu
Rinse
3.0 M
HNO3
241
Am
Strip
4.0 M
HCl
239
+
0.1 M
NaNO2
Pu
Strip
0.03 M
ammonium
oxalate
Background
10
lot TRA07164
-1
0
2
4
6
8
10
12
Bed Volumes
14
16
18
20
____________________________________________________________________
Jill Bernstein
Quality Control Chemist
Prepared: April 25, 2005
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Conclusions
• Eichrom is implementing a new QC program.
• The new QC program will include liquid-liquid
extraction tests (extractants), Dw tests (every resin
lot) and column elution tests (resin lots with new raw
materials).
• So far, TRU and TEVA from 2004 have been tested to
generate data from which metrics to evaluate new
resin lots will be determined.
• UTEVA and Sr Resin tests are next, followed by
DGA and the remaining Eichrom products.
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