eichrom technologies user’s group workshop … · eichrom technologies user’s group workshop...

EICHROM TECHNOLOGIES USER’S GROUP WORKSHOP DURING THE RRMC 2015

Workshop Chair: Terence O’Brien, [email protected]

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

Thank you for collaborating, asking, questioning, testing, pushing, buying and joining us today.

www.eichrom.com

What’s NEW with Eichrom

• 25th Anniversary Celebration – Founded February 1990

• Revised and New Methods

www.eichrom.com

New and Revised Methods

6

www.eichrom.com

Flow charts for easy method application

7

www.eichrom.com

Agenda for the Eichrom User’s Group Meeting


• Purity of DGA Normal for Po Separations – Daniel

McAlister


– Sherrod Maxwell

• Pb-Resin: New Approaches, Challenges, and

Troubleshooting


www.eichrom.com




• New Application Notes

www.eichrom.com

Application Notes

12

www.eichrom.com

Example of layout of application notes

13

www.eichrom.com

Separation and filter preparation

14

www.eichrom.com

Application Evaluation

15

www.eichrom.com

Agenda for the Eichrom User’s Group Meeting


• Purity of DGA Normal for Po Separations – Daniel

McAlister


– Sherrod Maxwell

• Pb-Resin: New Approaches, Challenges, and

Troubleshooting


www.eichrom.com

Break

www.eichrom.com




• New Application Notes

• Nuclear Medicine

www.eichrom.com

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

Quality: A Brief History Sarah McAlister RRMC 2015

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

http://www.rrmc.co/index.cfm

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 3 10-1 100 101

100

101

102

103

104

105

106

HNO3

HCl

k' Po on DGA Resin

k'

[Acid], M

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

Only Po???

What Changed? Can we purify?

How do we prevent?

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

0.01 0.1 11

10

100

k' - P

o

[HNO3], M

DNSR10A DNS031415 DNX100715 DNX073115

14

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 DGC

16

O

O

ClCl

O

O

O

OHHO

O

PCl3

PCl5 POCl3

H3PO4

HCl

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

Common DGA Impurities by LC-MS

18

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

5 5

Rapid Ra-226 Aqueous Sample Preparation

Wet-ash urine ppt

RRMC 2011

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

15

Blank Test using Cation + DGA Resin : Stacked elution

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

Ra-226 Results for Spiked Vegetation

19

5 g MAPEP blank vegetation, 8 hour count

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

Ra-228 Test Results

23

Ra-228 Test Results

24

Ra-228 Test Results

25

Ra-228 Test Results

26

Ra-228 Test Results

27

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


59.5% 5.43%

Tap Water

Pb-203 Tracer Only

1.33% 1.27%


30.7% 2.8%

• Three replicates of each matrix/condition group were analyzed.

Stable Lead Carrier Recovery

Matrix Condition Mean Chemical Yield

Standard Deviation


Stable Lead Carrier Only 12.4% 6.5%


18.0% 4.5%

River Water



85.9% 43.0%

Tap Water



19.7% 1.8% • Three replicates of each matrix/condition group were

analyzed.

Tracer vs. Chemical Yields

Matrix Condition Tracer Yield Chemical Yield



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?

Thanks! Questions?

Interdisciplinary Graduate Program in

HUMANTOXICOLOGY

Uranium Valence Control for analytical separations Daniel McAlister, Ph.D. Senior Chemist

http://www.rrmc.co/index.cfm

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

www.eichrom.com

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)

www.eichrom.com

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+

www.eichrom.com

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

www.eichrom.com

Better Scenario

7

Oxidizing Chemistry in Load Solution

Ti3+/Phosphate/Fluoride carryover from ppt


Oxidation prior to source preparation

High U yield + Clean Th Fraction

www.eichrom.com 8

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

www.eichrom.com 9


Load

Rinse

1

Rinse

2

Rinse

3

Th St

rip

TEVA

0.1

1

10

100

% U

3M HNO3-1M Al(NO3)3


6MHCl

www.eichrom.com 10


Load

Rinse

1

Rinse

2

Rinse

3

Th St

rip

TEVA

20

40

60

80

100

% U

3M HNO3-1M Al(NO3)3


9MHCl

www.eichrom.com


11

Load

Rinse

1

Rinse

2

Rinse

3

Th St

rip

TEVA

0.1

1

10

100

% U

3M HNO3-1M Al(NO3)3


9MHCl

www.eichrom.com

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)

www.eichrom.com

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%

www.eichrom.com

Summary

14

Oxidizing Chemistry in Load Solution

Many steps can be take to improve separations

Rinse to remove U(VI) – adding H2O2 may help


Add H2O2 prior to source preparation (except U)

www.eichrom.com

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-

www.eichrom.com

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

www.eichrom.com

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

www.eichrom.com

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)

www.eichrom.com

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

Initial Spectra

The MB:

3

The LCS:

Initial Spectra

The MB:

4

The SMP:

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

• 500 mL sample (preserved) • Ni and Fe carriers • Spike LCS (Ni-63)

7

Ni-63 Water Prep (cont’d)

• Hydroxide precipitation ~ Heat near boiling ~ Slowly add 10M NaOH

to pH ~8-9

8

• Centrifuge/discard supernate


• 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


• Load onto conditioned (pH 8-9 H20) Ni cartridge

10

• Rinse w/ 10 mL 0.2M C6H14N2O7


• 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

Spectral Comparison

Initial:

15

w/ 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!!

19

Questions/Contact Info

• Terry Romanko – Radiochemistry Technical Director

• St. Louis Laboratory • [email protected] • 314-298-8566

Questions?

eichrom technologies user’s group workshop … · eichrom technologies user’s group workshop...

Documents