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EICHROM TECHNOLOGIES USER’S GROUP WORKSHOP DURING THE RRMC 2015
Workshop Chair: Terence O’Brien, tobrien@eichrom.com
Current Speakers: Sherrod Maxwell1, Daniel McAlister2, Sarah McAlister2, Terence O’Brien2
plus others.
Affiliations: 1) Savannah River National Laboratory, 2) Eichrom Technologies
This year’s Eichrom User’s Group Workshop will be a special event as we are celebrating our
25th year. Our workshop will feature presentations by a number of respected scientists in the
radioanalytical community. Dr. Dan McAlister will be speaking on updates and revisions to the
Eichrom Method library. Our quality manger Sarah McAlister will be speaking on roll of
customer feedback on our quality systems over the years. Additionally, we will have talks by
many respected scientists who have used the Eichrom products. This year we will also have a
presentation by the Eichrom Scholar recipient.
We hope you will join us on Wednesday afternoon.
Eichrom Technologies User’s Group Meeting Held at the 61th RRMC Conference – Wednesday, 28 October 2015 Sheraton Iowa City Hotel Iowa City, IA
Welcome
www.eichrom.com
Eichrom User’s Group Meeting
• Quality, A Brief History – Sarah McAlister
• Purity of DGA Normal for Po Separations – Daniel McAlister
• Rapid Methods for Ra-226 and Ra-228: An Update
– Sherrod Maxwell
• Pb-Resin: New Approaches, Challenges, and Troubleshooting
– Dustin May, Andrew Nelson, Michael Schultz
• Uranium Valence Control for Analytical Separations
– Daniel McAlister
• Removal of Tc-99 Interference from Ni-63 Analysis of Water
Sample – Terry Romanko
• Additional Questions and Answers – You, Our Customers
www.eichrom.com
Eichrom Technologies
Michael Fern President
Shari Tegel Director of Finance and Administration
Joel Williamson Director of Operations
J van de Linde Director of Sales
Jill Bryant Quality System Coordinator
Daniel McAlister, Ph.D. Senior Chemist
Sarah McAlister Quality Manager
Terence O’Brien Technical Sales Scientist
Phil
www.eichrom.com
What’s NEW with Eichrom
• 25th Anniversary Celebration – Founded February 1990
• Revised and New Methods
www.eichrom.com
Agenda for the Eichrom User’s Group Meeting
• Quality, A Brief History – Sarah McAlister
• Purity of DGA Normal for Po Separations – Daniel
McAlister
• Rapid Methods for Ra-226 and Ra-228: An Update
– Sherrod Maxwell
• Pb-Resin: New Approaches, Challenges, and
Troubleshooting
– Dustin May, Andrew Nelson, Michael Schultz
www.eichrom.com
What’s NEW with Eichrom
• 25th Anniversary Celebration – Founded February 1990
• Revised and New Methods
• New Application Notes
www.eichrom.com
Agenda for the Eichrom User’s Group Meeting
• Quality, A Brief History – Sarah McAlister
• Purity of DGA Normal for Po Separations – Daniel
McAlister
• Rapid Methods for Ra-226 and Ra-228: An Update
– Sherrod Maxwell
• Pb-Resin: New Approaches, Challenges, and
Troubleshooting
– Dustin May, Andrew Nelson, Michael Schultz
www.eichrom.com
What’s NEW with Eichrom
• 25th Anniversary Celebration – Founded February 1990
• Revised and New Methods
• New Application Notes
• Nuclear Medicine
www.eichrom.com
Continuing Agenda for the Eichrom UGM
• Uranium Valence Control for Analytical Separations
– Daniel McAlister
• Removal of Tc-99 Interference from Ni-63 Analysis of
Water Sample – Terry Romanko
• Additional Questions and Answers – You, Our
Customers
www.eichrom.com
• Thank You for attending the Eichrom User’s Group Meeting at the 61th Radiobioassay and Radiochemical Measurements Conference
• Please take some time and discuss your work area needs
• Conference Dinner
www.eichrom.com
What is Quality Control?
• ISO – International Organization for Standardization • Quality Control (QC) – “…focused on fulfilling
requirements.” 1 Ex. Inspections & Testing of Products
Eichrom QC Examples
www.eichrom.com
How old is quality control?
• It is hard to say… Quality control is everywhere and in our nature.
• Natural Selection - If you believe in this, it is a great example of quality control.
www.eichrom.com
Historical Examples of Quality Control
• Flints used to carve alder or limewood Dugout Canoes (~3500 B.C. in Denmark)2
The excavation of a mine revealed a discarded parts pile.
www.eichrom.com
Historical Examples of Quality Control, continued
• Cubit – First measurement of length.
• The Royal Egyptian Cubit was
to be calibrated against a precision standard (Royal Cubit Master) at regular intervals. “Failure to do so was punishable by death.”3
www.eichrom.com
Components of Quality Management
• Quality Control –
• Quality Assurance (QA) – “…focused on providing confidence that quality requirements will be fulfilled.” 1 Code of Hammurabi (3000 B.C. in Babylonia)
“The mason who builds a house which falls down and kills the inmate shall be put to death.”4
Eichrom QA Examples
www.eichrom.com
Components of Quality Management cont.
• Quality Planning – “…focused on setting quality objectives and specifying necessary operational processes and related resources to achieve the quality objectives.”1
• Quality Improvement – “…focused on increasing the ability to fulfill quality requirements.”1 Kaizen, Six Sigma, Lean Manufacturing, etc.
• 3500BC → 21st Century • Quality Control → Quality Management
www.eichrom.com
Quality Related Historical Events
Life Changing Events
• 1775-1783 American Revolution
• 1914-1918 World War I
• 1939-1945 World War II
• 1945 1st Atomic Bomb (Trial and Warfare)
• 1954 1st Commercial Nuclear Power Plant
• 1979 Three Mile Island
• 1986 Chernobyl
• 2011 Fukushima Daiichi
Measurements and Standards
• 1781-1789 Articles of the Confederation
• 1789 United States Constitution
• 1790 Jefferson Report
• 1830 Office of Standard Weights and Measures
• 1901 National Bureau of Standards
• 1988 NIST
Quality
Eichrom Technologies
1783 US Customary Units (after revolution)
1960 International System / Metric (SI Units)
1930s Statistical QC (SQC – Control Charts) 1947 ISO Founded 1950s Total Quality Control 1968 Japanese (Companywide QC) 1971 OSHA / NIOSH Founded 1987 ISO QM Standard 1994 ISO 9001:1994 2000 ISO 9001:2000 2008 ISO 9001:2008 2015 ISO 9001:2015
1976 NPO Founded 1981 NPO NIOSH Certified 1990 Eichrom Founded 1995 Eichrom ISO Certified 2008 NPO Acquired by Eichrom 2010 NPO ISO Certified
www.eichrom.com
Document, document, document
• Is it really worth doing if you don’t write it down?
• How to manage all of the data?
– 20th Century – Manufacturing Industry / Quality Advancements – 21st Century – Electronic Industry
www.eichrom.com
Quality Management Software
• Quality Collaboration by Design (QCBD -- Access database) – Customer Comment – Corrective and Preventive Action – Equipment Management – Master List and Change Management – Nonconformance Control – Process Deviation – Vendor Management – Training Management
www.eichrom.com
Why?
• Eichrom’s commitment to the radiochemistry community to provide analytical separation products that the world can count on.
– “Do it right the first time”
– “Do it today, not tomorrow” Mike Fern, President of Eichrom
www.eichrom.com
Works Cited
1 Hoyle, David. ISO 9000 Quality Systems Handbook. 4th ed. Great Britain: Butterworth-Heinemann, 2001. Print.
2 Juran, Joseph M. A History of Managing for Quality: The Evolution,
Trends, and Future Directions of Managing for Quality. USA: ASQC Quality Press, 1995. Print.
3 Nemeroff, Edward. A Standards, Metrology, Conformity Assessment and The TBT Agreement: A Desk Top Reference Handbook. http://pdf.usaid.gov/pdf_docs/Pnadp635.pdf
4 Omachonu, Vincent K. and Joel E. Ross. Principles of Total Quality. 3rd ed. USA: CRC Press, 2004. Print.
Purity of DGA Normal for Po Separations
Daniel McAlister, Ph.D. Senior Chemist Ed Rush Chemist
www.eichrom.com
DGA Applications
2
N
O
O N
O
RR
RR
Rare Earth Separations1
Trivalent Actinides1
Removal of alpha emitters from Ra2
Polonium Separations3
1Horwitz, McAlister, Bond, Barrans, Jr., Solv. Extr. Ion Exch., 23, 319 (2005) 2Maxwell, Culligan, Hutchinson, Utsey, McAlister, J. Radioan. Nucl. Chem. 300(3), 1159 (2014) 3Mawwell, Culligan, Hutchinson, Utsey, McAlister, J. Radioan. Nucl. Chem. 298(3), 1977 (2014)
www.eichrom.com
DGA Quality Control
4
2009 and earlier: Elution of Eu-152 Tracer Periodic LC-MS
2010-2015: Separation of Am-241 and U-233
2015 and later: Add Po QC test
www.eichrom.com 5
DNS0
9220
9DN
S092
409
DNS0
2101
0DN
S082
610
DNS0
3011
1DN
S042
211
DNA0
4261
1DN
S081
511
DNS1
0191
1DN
S040
312
DNS0
9241
2DN
S022
513
DNS0
5101
3DN
S091
613
DNS1
0251
3DN
S090
614
DNS1
1131
4DN
S031
415
DNS0
5051
5
0
20
40
60
80
100
Po R
ecov
ery
in 2
0mL
0.05
M H
NO3
Polonium Recovery on TODGA
Pur
ifica
tion
www.eichrom.com
Synthesis of DGA from Diglycolyl chloride (DGC)
7
O
O
ClCl
O
NHRR
+THF
NR'
R'R'
+
O
O
NN
O
RR
RR
NR'
R'R'HCl
Horwitz, McAlister, Bond, Barrans, Jr., Solv. Extr. Ion Exch., 23, 319 (2005) Sasaki, Sugo, Suzuki, Tachimori, Solv. Extr. Ion Exch., 19, 91 (2001)
www.eichrom.com
Raw Materials
8
Purchased a large amount of DGC in 2011 - Synthesis Chemist noted darkening of material over time - Dark material was not a problem in the past - Dark material persists into final product - Impurity is heat/pH sensitive
Supplier began packing Dioctylamine in plastic (was glass) - Plastic containers frost over (amine + air/moisture)
Po issue not observed with TEHDGA - Is dioctylamine the source of the issue?
www.eichrom.com
Distill Diglycolylchloride
Improved Synthesis and Purification
9
Distill Dioctylamine
Test Po recovery. Additional purification as necessary. Full batch and standard QC.
Dry Solvent
www.eichrom.com 10 DNS0
2101
0DN
S082
610
DNS0
4261
1DN
S030
111
DNS0
4271
1DN
S081
511
DNS1
0191
1DN
S040
312
DNS0
9241
2DN
S022
513
DNS0
5101
3DN
S091
613
DNS1
0251
3DN
S090
614
DNS1
1131
4DN
S031
415
DNS0
5051
5
0.0
0.2
0.4
0.6
0.8
1.0
96.096.597.097.598.098.599.099.5
100.0
Am in U fraction
% A
m Re
cove
ry
Am Yield
Am in Standard DGA QC
www.eichrom.com 11 DNS0
2101
0DN
S082
610
DNS0
4261
1DN
S030
111
DNS0
4271
1DN
S081
511
DNS1
0191
1DN
S040
312
DNS0
9241
2DN
S022
513
DNS0
5101
3DN
S091
613
DNS1
0251
3DN
S090
614
DNS1
1131
4DN
S031
415
DNS0
5051
5
0.0
0.2
0.4
0.6
0.8
1.0
96.096.597.097.598.098.599.099.5
100.0
U in Am fraction
% U
Rec
over
y
U Yield
U in Standard DGA QC
www.eichrom.com
Title and Content slide
12
DNX0
3027
DNX0
3277
DNX0
4117
DNX0
8177
DNX0
8247
DNX0
3278
DNX0
4098
DNX0
4148
DNX0
5208
DNX0
6138
DNX0
6168
DNX0
8050
9DN
X051
209
DNX0
6100
9DN
X061
609
DNX1
0120
9DN
X101
209-
2DN
X101
309
DNX1
0140
9DN
X093
110
DNX0
9011
0DN
X060
611
DNX0
7191
1DN
X090
512
DNX0
6031
3DN
X080
114
DNX0
4211
5
0.1
1
10
100
Po (0.05M HNO3) U (0.1M HNO3) Am (3M HCl)
k'
k’ on DGA Resin Lots
www.eichrom.com
Title and Content slide
13
0 1 2 3 4 5 6 7 8 9 10 11101
102
103
104
105
dpm
Cf-2
52
mL 0.1M HCl
2010 (Good) 2015 (Worst) 2015 (Cleaned)
Elution of Cf-252 from 2mL DGA, Normal Cartridges
www.eichrom.com
Synthesis and Degradation of DGC
15
O
O
ClCl
O
O
O
OHHO
O
SOCl2 SO2 HCl
Aged samples of SO2Cl2 develop a yellow hue, possibly due to the formation of S2Cl2.
S2Cl2 has been used to introduce C-S bonds.
www.eichrom.com
Synthesis and Degradation of Dioctylamine
17
n R OH NH3+ RnNH3-n H2O+
n R X NH3+ RnNH3-n nXH+ NH3
Octylamine impurity?
Hydrolysis/Oxidation by air/water?
www.eichrom.com
Elemental Analysis of DGA Lots
19
Lot
(74.4%)
C (12.5%)
H (8.3%)
O (4.8%)
N S P
DNX090512 (Good) 74.6 12.8 8.4 4.9 0.07 <25ppm
DNX060915 (OLD DGC) 74.6 12.4 8.3 4.8 0.1 <25ppm
Impurity from Column 67.7 11.8 14.3 5.5 <0.05 <25ppm
DNX073115 (NEW DGC) 74.8 12.9 8.4 4.8 <0.05 <25ppm
C = 67.4% O = 13.5% H = 11.3% N = 7.9% C = 67.0% O = 17.9% H = 11.0% N = 3.9% C = 69.4% O = 13.2% H = 11.6% N = 5.8%
O
N O
O
NHOOct
OctOct
www.eichrom.com
• DGA Synthesis and Purification Improved • DGA QC updated with Po testing • DGA lots from 2010-2015 tested retroactively
– Standard Separations – Po Separations
• Only separation affected by impurity – Other customer separations (as comments received) – Data available upon request
Summary
20
Rapid Methods for Ra-226 and Ra-228: An Update
Sherrod L. Maxwell Senior Fellow Scientist
61st Annual Radiobioassay and Radiochemical Measurements Conference October 28, 2015
Outline
• Ra-226 in water – Can we apply the approach we used for urine? – PO4-3 vs. CO3-2
– Ba-133 vs. Ra-225 tracer – DGA Resin instead of Ln Resin?
• Ra-226 in vegetation – Fusion?
• Ra-228 in water – Immediate collection of Ac-228 vs. Ingrowth
2
3 3
Background
• Need for rapid radiochemical methods – Emergency response
• Radiological event • Rapid turnaround times • High capacity
• Ra-226 – in hospitals, laboratories – alpha emitter, 4.78 MeV (94.5%), 4.61 MeV (5.55%) – 1600 year half-life (alpha spectrometry and ICP-MS) – radiotoxic, follows calcium in food chain into bones
• Urine Maxwell S, Culligan B, Hutchison J, Utsey R and McAlister, D (2014) Rapid determination of 226Ra in emergency urine samples. Journal of Radioanalytical and Nuclear Chemistry, online first, Feb. 2014
Risk from Ra-226
• More dangerous “dirty bomb” than Uranium RDD – Delivers much higher dose
• Besides RDD… – Risk of addition at post-treatment water supply
• Ra-226 has been trafficked repeatedly in different countries – Po-210 has already been used successfully for a criminal act
• Risk Due to Radiological Terror Attacks With Natural Radionuclides – Steinhäusler Friedrich, Rydell Stan, and Zaitseva Lyudmila – Citation: AIP Conference Proceedings 1034, 3 (2008); doi: 10.1063/1.2991254
4
6 6
Ra-225 Tracer Decay
Rapid Radiochemical Methods for Selected Radionuclides in Water for Environmental Restoration Following Homeland Security Events, EPA 402-R-10-001 February 2010
Works well, but may require Th-229/Ra-225 milking
Water Samples
• Ba-133 tracer may be very useful – No waiting for ingrowth – No need to remove stable Ba (as with soil) – Allows for Ra-224 assay – Assurance Ba/Ra are in sync can be managed (no divergence) – No milking of Th-229/ lower blanks – Less chance of detector contamination
• But – 2 counts are needed (gamma count can be very short)
7
SRNS Approach
• Use calcium phosphate instead of calcium carbonate – Slight Ra-226 contamination in sodium carbonate – Need low blanks – Lower solubility of calcium phosphate – lower Ca needed
• Less Ca less cation resin less volume less time
• Use stacked elution with Cation resin+ DGA Resin to save time
8
9
0 5 10 15 20 25 30 35 40 45 5010-1
100
101
102
103
104
105
Strip5M
HNO3
Rinse3MHCl
co
unts
mL
Load 1M HCl +50 mg Ca +Ba-133 andRa-223
0.6% ofBa-133
Rinse1MHCl
Elution on 3.0 g of 50Wx8, 200-400 mesh
Ba and Ra Behavior on Cation Resin
10
Rapid Sample Preparation for Ra-226 in Water
Less Ca, PO4 instead of carbonate
200 mL water
Add *133Ba as Tracer
Add 50mg Ca, 3mL 3.2M (NH4)2HPO4,
14.5M NH4OH until ~pH 10
Mix well, wait 5 min. and centrifuge @~3500
rpm for 6 min.
Discard supernate
Add 10mL 1.5M HCl, 7 ml 1.5M HCl to dissolve solids and add to tube
Column Load Solution
*225Ra can also be used
11
Sulfuric acid can be used instead
Column Load Solution
3g Cation Resin
(200-400 mesh)
Rinse Column with 15mL of 3M HCl
(Removes Ca, Pb, Bi, U)
Add DGA Cartridge and Elute 226Ra from
Cation Resin with 20mL 5M HNO3
Add 5mL 5M HNO3 to DGA Resin* and
collect 226Ra
Transfer eluent to 250 mL glass beaker and evaporate to dryness, adding 3mL 30wt% tube rinse to beaker. Redissolve in 10 ml 1.5 M HCl, heat to dissolve, and transfer to 50 ml tube. Rinse beaker with two 5ml
volumes of 1.5 M HCl, warming to rinse well.
Remove Cation Resin and discard
Ra: Add 3mL conc. HCl, 3g (NH4)2SO4,
50µg Ba+5ml isopropyl, ice 15 min.
*DGA Resin -removes Bi, Pb, Th,
U, Po isotopes
Alpha
Spectrometry
Rapid Column Separation for Ra-226 in water
Combine final DGA purification with cation resin elution!
12
Rapid Separation using Cation + DGA Resin : stacked elution
2 pCi in 200 ml aliquot = 10 pCi/L DI Water
13
Rapid Separation using Cation + DGA Resin : stacked elution
4 pCi in 200 ml aliquot = 20 pCi/L ATP water
14
Rapid Column using Cation + DGA Resin : stacked elution
0.1 pCi in 200 ml aliquot = 0.5 pCi/L DI Water
Ra-226 in Vegetation
• Weigh 5g vegetation in 250 ml Zr crucible • Add Ba-133 tracer • Ramp from 300C to 600C; remove crucibles • Wet ash with HNO3/H2O2 briefly on hotplate • Fuse samples with 10g NaOH at 600C • Transfer to 225 ml tube…150 ml volume with water
16
Ra-226 in Vegetation
• Add 10 ml 12M HCl, mix • Add 100 mg Ca and 10 ml 2M sodium carbonate and mix. • Wait 10 minutes, centrifuge 5 minutes. • Dissolve ppt in 1M HCl, some HF (as needed) to dissolve Si solids • Ready for cation resin
• Less redissolution problems than with phosphate ..... – but need to minimize carbonate to keep blanks low
17
Cation Resin + DGA Resin Rapid Purification
• Load 20 ml 1-1.5M HCl with trace HF to 5g cation resin • 30 ml 3M HCL rinse (to remove Ca) • Add DGA Resin • 20 ml 5M HNO3 elution through DGA • Convert to HCl, BaSO4 micro-ppt.
• Tested with 5g MAPEP blank vegetation material • Plan to test with foods….
18
What about Ra-228 in water?
• Immediate collection of Ac-228 • Some challenges with complete elution of La/Ac from Cation resin
and behavior of Ac/La DGA Resin • Wanted to make more rugged
20
Ra-228 Update
• Updated our Ra-228 method • La carrier for yield • 1L sample aliquot • CO3 -2 ppt enhanced with PO4
-3 • Load to 5g cation resin and remove Ca with 3M HCl • Elute Ra-228 and La with 8M HNO3 • Wait 36 hours for Ac-228 ingrowth • Load Ra-228 to DGA Resin from 6M HNO3. Modified rinses slightly. • Elute with 2M HCl and measure La yield via ICP-MS • Count AcF3 on 25 mm filter by gas flow proportional counting
21
Enhancements
• Wait on Ac-228 ingrowth
– Reduces large volume of cation elution (7M HNO3 ) passing directly through DGA Resin (stacked)
– Elute Ra/La from cation resin with 30
ml 8M HNO3, evaporate, wait 36 hours, redissolve in small load solution (6M HNO3)
22
10-1 100 10110-1
100
101
102
103
104
k' Ra <1 for all [Acid], M
HCl
k' Ac(III) on TODGA Resin
k'
[Acid], M
HNO3
Summary
• Rapid Methods for Ra-226 – Rapid assessment of radiological impact is critical – Mitigate dose and protect the public and environment – Maintain public trust – Lowers costs of routine operations
• Improvements in Ra-226 methods for water and vegetation samples – <4-5 hours with simultaneous sample preparation – Ba-133: No waiting for Ra-225 in-growth – Allows Ra-224 measurement – Can be adapted to smaller or larger water aliquots as needed
• Improvements in Ra-228 – Improved ruggedness with Ac-228 ingrowth, then loading to DGA Resin
28
Pb-Resin: New Approaches, Challenges, and
Troubleshooting Dustin May, Andrew W. Nelson,
Michael K. Schultz
Interdisciplinary Graduate Program in
HUMANTOXICOLOGY
Older Methods with Pb-Resin
• Two similar methods – ASTM D7538 – Eichrom Pb-210 and Pb-210 in Water OTW01 (Pre
5/1/2014) • Iron Hydroxide preconcentration • Load on Pb-Resin or Sr-Resin in 1 M HNO3 • Strip Pb with 20 mL H2O • H2SO4 precip • Gas Flow
Rationale for ASTM D7538
• Highly respected organization
• Highly regarded and widely used methods
• Validated by interlab comparisons
• Very similar to Eichrom method
Problems with 210Pb Methods
• Recovery based on mass – Unknown quantities of
stable Pb in samples – Drifting analytical
balances – Must have exceptionally
pure separations – Affected by humidity
• Stable Pb carrier – How much background
is in Pb carrier? – Requires more resin – Requires H2SO4
Introducing, Pb-203 • Pb-203
– Cyclotron produced – EC, screaming
gammas – t1/2 = 52 hours
• “massless” tracer
• Can measure on the column!
• Do not need to consider endogenous Pb
• Drifting analytical balances no longer a problem
• May be able to use smaller quantities of resin per sample? – more samples
Experimental Conditions
• Fracking flowback fluid, river water, and tap water were utilized
• Each matrix was analyzed under the following conditions: Pb-203 tracer/stable Pb carrier, Pb-203 tracer only, and stable Pb carrier only
• Matrix/condition pairs were analyzed in triplicate in accordance with ASTM D7538
Pb-203 Tracer Recovery
Matrix Condition Mean Tracer Yield Standard Deviation
Fracking Flowback Fluid
Pb-203 Tracer Only
21.1% 14.9%
Stable Lead Carrier & Pb-203 Tracer
27.3% 7.8%
River Water
Pb-203 Tracer Only
ND
Stable Lead Carrier & Pb-203 Tracer
59.5% 5.43%
Tap Water
Pb-203 Tracer Only
1.33% 1.27%
Stable Lead Carrier & Pb-203 Tracer
30.7% 2.8%
• Three replicates of each matrix/condition group were analyzed.
Stable Lead Carrier Recovery
Matrix Condition Mean Chemical Yield
Standard Deviation
Fracking Flowback Fluid
Stable Lead Carrier Only 12.4% 6.5%
Stable Lead Carrier & Pb-203 Tracer
18.0% 4.5%
River Water
Stable Lead Carrier Only 25.6% 6.0%
Stable Lead Carrier & Pb-203 Tracer
85.9% 43.0%
Tap Water
Stable Lead Carrier Only 20.7% 3.2%
Stable Lead Carrier & Pb-203 Tracer
19.7% 1.8% • Three replicates of each matrix/condition group were
analyzed.
Tracer vs. Chemical Yields
Matrix Condition Tracer Yield Chemical Yield
Fracking Flowback Fluid
Stable Lead Carrier & Pb-203 Tracer
27.3 ± 7.8% 18.0 ± 4.5%
River Water Stable Lead Carrier & Pb-203 Tracer
59.5 ± 5.4% 85.9 ± 43.0%
Tap Water Stable Lead Carrier & Pb-203 Tracer
30.7 ± 2.8% 19.7 ± 1.8% • Three replicates of each matrix/condition group were
analyzed.
Recovery Discussion
• Recoveries vary wildly across samples – Large standard deviations
• The Pb-203 was measureable on the column post elution step – Lead was loaded and retained on the resin, but
not eluted
UIowa Recovery
• Soil Recoveries – 81 samples – Average: 75% ± 9 % – Range: 49% - 105%
• Note, these were prepared by Eichrom Pb in Soil Method
• Water Recoveries – 8 samples – Average: 76% ± 10 % – Range: 62% - 91%
• Note, these values were prepared by ASTM D7538 on flowback/produced fluids from the Niobrara formation
Hypotheses About Recovery Issues • pH seems a likely cause of the variation
– UI Chemistry Lab uses house deionized water – SHL uses house deionized water that is then run through a
Millipore purification system – Incomplete rinsing of loading solutions could lead to
lowered pH in an un-buffered system • Stable lead carrier could actually be necessary for
effective elution • Same operator, minimize sources of variation
Water Source pH
UI Chemistry Lab 8.1
SHL at UI 6.0
Immediate Plans
• Repeat experiment using buffered eluent solution recommended by current Eichrom method
• We would like to open it up to suggestions on method and experimental improvements
Future Directions
• Revision of ASTM method D7538 • Place a caution on Eichrom method for those that
want to use water • Possible develop single sample Pb-Po prep for
alpha spec by SR Resin?
Uranium Valence Control for analytical separations Daniel McAlister, Ph.D. Senior Chemist
www.eichrom.com
Issue
• Unexpected Behavior of U and/or Pu
2
• Low U yields
• U in Th fractions
• Incomplete reduction/oxidation of Pu
• Complex system:
– Al(NO3)3/HNO3
– Sulfamic Acid
– TiCl3 Fe(II) Ascorbic Acid
– NaNO2 H2O2
– Phosphate/Fluoride
– Sample Matrix
www.eichrom.com
Common Separation Schemes
3
Reducing Oxidizing
Th(IV) Np(IV)
Am/Cm(III) Pu(III) U(VI)
Th(IV) Pu(IV) Np(IV)
Am/Cm(III) U(VI)
Test Factors that could: -Yield unexpected oxidation states -Lead to poor recoveries -Lead to poor separations
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U on TEVA
4
0.1 1 1010-2
10-1
100
101
102
103
104
105
U(VI)
Th(IV)
k'
[HNO3], M
Pu(IV)
0.1 1 1010-2
10-1
100
101
102
103
104
105
U(IV)
U(VI)
Th(IV)k' <1
k'
[HCl], M
Pu(IV)
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Reduction of U(VI) to U(IV) by ferrous iron
5 C.F. Baes, Jr. “The reduction of Uranium(VI) by Ferrous Iron in Phosphoric Acid Solution: The formal electrode potentional of the U(IV)/U(VI) couple,” Oak Ridge National Laboratory, ORNL 1581 (1953)
U4+ + 2Fe3+ + 2H2O <--> UO22+ + 2Fe2+ + 4H+
UO22+ + 2Ti3+ <--> U4+ + 2TiO2+
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Worst Case Scenario
6
Reducing Chemistry in Load Solution
Ti3+/Phosphate/Fluoride carryover from ppt
Strip Th with 6M HCl
No oxidation prior to source preparation
Low U yield + U in Th Fraction
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Better Scenario
7
Oxidizing Chemistry in Load Solution
Ti3+/Phosphate/Fluoride carryover from ppt
Strip Th with 9M HCl
Oxidation prior to source preparation
High U yield + Clean Th Fraction
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U on TEVA (6M HCl Th Strip)
Load
Rinse
1
Rinse
2
Rinse
3
Th St
rip
TEVA
20
40
60
80
100
% U
3M HNO3-1M Al(NO3)3
3mg Fe/Ascorbic/Sulfamic 2mL 0.6M Ferrous Sulfamate Ferrous Sulfamate/NaNO2
6MHCl
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U on TEVA (6M HCl Th Strip)
Load
Rinse
1
Rinse
2
Rinse
3
Th St
rip
TEVA
0.1
1
10
100
% U
3M HNO3-1M Al(NO3)3
3mg Fe/Ascorbic/Sulfamic 2mL 0.6M Ferrous Sulfamate Ferrous Sulfamate/NaNO2
6MHCl
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U on TEVA (9M HCl Th Strip)
Load
Rinse
1
Rinse
2
Rinse
3
Th St
rip
TEVA
20
40
60
80
100
% U
3M HNO3-1M Al(NO3)3
3mg Fe/Ascorbic/Sulfamic 2mL 0.6M Ferrous Sulfamate Ferrous Sulfamate/NaNO2
9MHCl
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U on TEVA (9M HCl Th Strip)
11
Load
Rinse
1
Rinse
2
Rinse
3
Th St
rip
TEVA
0.1
1
10
100
% U
3M HNO3-1M Al(NO3)3
3mg Fe/Ascorbic/Sulfamic 2mL 0.6M Ferrous Sulfamate Ferrous Sulfamate/NaNO2
9MHCl
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Alpha Spectra (Th-229 + U-233, 6M HCl Th Strip)
12
Add H2O2!!!!!
50mg CeF3 no H2O2
50mg CeF3 50uL H2O2
233U (4.79-4.82 MeV)
229Th (4.81-5.05 MeV)
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Other Factors (U in 6M HCl)
13
System No NaNO2 Add NaNO2
1% TiCl3 9-11% 0.2-0.3%
LaF3/TiCl3 2-3% 0.1-0.2%
Ferrous Sulfamate 1-8% 0.1-1.0%
Ca/PO43- 2-3% 0.1-0.2%
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Summary
14
Oxidizing Chemistry in Load Solution
Many steps can be take to improve separations
Rinse to remove U(VI) – adding H2O2 may help
Strip Th with 9M HCl
Add H2O2 prior to source preparation (except U)
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Valence Adjustment Schemes (TiCl3 Reduction/ppt)
15
Ti3+
Ti3+ Ti3+
Ti3+
U(IV)
Th(IV)
Pu(III)
Am(III) T.W. Newton“The Kinetics of the Oxidation-Reduction Reactions of U, Np, Pu, Am in Aqueous Solutions,” LANL TID-26506, (1975)
Pu4+ + Ti3+ + H2O <--> Pu3+ + TiO2+ + 2H+
UO22+ + 2Ti3+ <--> U4+ + 2TiO2+
Ti3+ PO43- F-
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Valence Adjustment Schemes (HNO3 Dissolution)
16 Morse, Edelstein, Fuger, “The Chemistry of the Actinide and Transactinide Elements,” 3rd Edition, Vols 3 and 4, Springer (2006).
Actinide (TiCl3)
Precipitation
Th(IV) Th(IV)
U(IV/VI) U(IV)
Np(IV/V/VI) Np(IV)
Pu(III/IV/VI) Pu(III)
Am/Cm(III) Am/Cm(III)
NO3- + 3H+ <--> HNO2 + H2O
NO3- + H2O + 2e-
<--> NO2- + 2-OH
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Valence Adjustment Schemes (Ferrous/Sulfamate/Ascorbic acid)
17 I.L. Jenkins “Factors Governing the Choice of a 237Np/238Pu Separation Process,” Actinides Reviews, 1, 187 (1969).
HNO2 + H3NSO3 → H2SO4 + N2 + H2O
OOH
HO O
OHHO
+ 2Fe(III) ↔ 2Fe(II) + 2H+ + O
OHHO O
OO
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Valence Adjustment Schemes (Ferrous/Sulfamate/Ascorbic acid)
18
U4+ + 2Fe3+ + 2H2O <--> UO22+ + 2Fe2+ + 4H+
Pu4+ + Fe2+ <--> Pu3+ + Fe3+
PuO22+ + Fe2+ <--> PuO2
+ + Fe3+
PuO2+ + Fe2+ + 4H+ <--> Pu4+ + Fe3+ + 2H2O
T.W. Newton“The Kinetics of the Oxidation-Reduction Reactions of U, Np, Pu, Am in Aqueous Solutions,” LANL TID-26506, (1975)
Np(IV)
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Valence Adjustment Schemes (NaNO2)
19
Fe2+ + NO2 <--> Fe3+ + NO2-
Pu3+ + NO2 <--> Pu4+ + NO2-
HNO2 <--> NO2 + NO + H2O
H+ + NO2- <--> HNO2
H+ + HNO2 + NO3- <--> 2NO2 + H2O
HNO2 + H3NSO3 → H2SO4 + N2 + H2O
Ascorbic acid + 2NO2 <--> 2H+ + 2NO2
- + Dehydroascorbic acid
A. Brunstad, “Oxidation of Plutonium(III) by Sodium Nitrite, Hanford Atomic Products Operation, Richland, Washington, HP-51655 (1957)
Proprietary and Confidential
Removal of Tc-99 Interference from Ni-63 Analysis of Water Sample
Terry Romanko Technical Director TestAmerica St. Louis
Eichrom User’s Group Workshop, RRMC 2015
2
Overview
• Client water sample submitted for analysis of Ni-63 exhibited unusual peak/shape in LSC spectrum
• Desire to report without interference
• Ni-63
~ 100 year half-life ~ Beta emitter ~ 65.87 keV Max; 17.13 keV Avg
5
What do we know?
• Client unable to provide much information regarding chemical composition of this well water
• No time to perform characterization • Spectrum similar to Tc-99 (different
cocktail mix) • Well has shown elevated gross beta and
Tc-99 in past. No Sr-90 of note. • Nitrate < 7 mg/L; VOA “ND”
6
Assumption
• We will proceed with (fairly good) assumption that interference is caused by Tc-99
• Assume that typical chemistry is used.
Ni-63 Water Prep (cont’d)
• Hydroxide precipitation ~ Heat near boiling ~ Slowly add 10M NaOH
to pH ~8-9
8
• Centrifuge/discard supernate
Ni-63 Water Prep (cont’d)
• Dissolve sample residue in 10 mL 1M HCl
9
• Add 1 mL 1M ammonium citrate (dibasic) ~ Gently heat, then allow to cool
• Add drop(s) 4% thymol blue ~ Adjust pH to ~8-9 w/ NH4OH (blue color) ~ +1mL 1M C6H14N2O7 if still cloudy
Ni-63 Water Prep (cont’d)
• Load onto conditioned (pH 8-9 H20) Ni cartridge
10
• Rinse w/ 10 mL 0.2M C6H14N2O7
Ni-63 Water Prep (cont’d)
• New collection tube, elute with 3 x 1mL portions of 3M HNO3;
• Bring to 4 mL w/ DI • 0.1 mL to metals for chemical recovery • Load into 15 mL Ultima Gold AB
Initial Water Prep
Water Sample Add carriers
Heat, 10M NaOH to pH ~8-9
hydroxide coppt
Cool, Settle, Centrifuge
10 mL 1M HCl, C6H14N2O7, Heat
4% thymol blue, NH4OH, pH to ~8-9
Load onto conditioned Ni
Resin
12
Rinse w/10 mL 0.2M C6H14N2O7
Elute w/ 3 x 1 mL 3M HNO3; to 4 mL
w/ DI H20
Add Cocktail; Count by LSC
Additional Step
• Additional Step added for removal of the Tc-99 ~ After initial pre-concentration, before loading on Ni
cartridge ~ Dissolve solids/residue with 1M HNO3 ~ Load on TEVA resin, collect eluant ~ Evap. to dryness
Additional Step
Water Sample Add carriers
Heat, 10M NaOH to pH ~8-9
hydroxide coppt
Cool, Settle, Centrifuge
10 mL 1M HCl, C6H14N2O7, Heat
4% thymol blue, NH4OH, pH to ~8-9
Load onto conditioned Ni
Resin
14
Rinse w/10 mL 0.2M C6H14N2O7
Elute w/ 3 x 1 mL 3M HNO3; to 4 mL
w/ DI H20
Add Cocktail; Count by LSC
TEVA Cleanup
16
Hindsight, Thoughts
• The lab originally prepped the sample without hydroxide co-precipitation; used evaporative concentration option of SOP instead.
• Ferric hydroxide co-precipitation should not carry pertechnetate. Thus, it is possible if this had been the pre-concentration used the TEVA cleanup may not have been necessary.
• Tc(IV) does follow ferrous hydroxide if effective reducing agent present.
• The sample may have reducing effects (unknown), so without some step to ensure the sample is oxidized, TEVA may be necessary.
17
Lessons
• Spectral review in an important part of the analysis process
• TEVA is an effective means to remove Tc-99 from well water samples
• Obtaining “process knowledge” from the client can often help decision-making process for handling apparent interferences or matrix issues
• Thorough interview of analysts is prudent when solving analysis issues
18
Special Thanks
Special thanks to: • Dan McAlister, Eichrom Technologies
• Terry O’Brien, Eichrom Technologies
Both have been more than generous with their resources!!
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