automated radiochemistry efforts at llnl

Lawrence Livermore National Laboratory, P.O. Box 808, Livermore, CA 94551

This work was performed under the auspices of the U.S. Department of Energy byLawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Automated Radiochemistry Efforts at LLNL

Performance Measures x.x, x.x, and x.x

Presented to:

Periodic Table of D.I. Mendeleev. The new superheavy elements

January 21, 2009

Roger A. Henderson, Kenton J. Moody, Dawn A. Shaughnessy, and Julie M. Gostic*

Chemistry, Materials, Earth, and Life Sciences DirectorateLawrence Livermore National Laboratory

*University of Nevada-Las Vegas

LLNL-PRES-406833

LLNL-PRES-406833


Chemistry Desires for Automation• Speed• Reproducibility• Lower Dose to Operators

Begin with a Heavy Element application• Single Column chemistry

Automated column regeneration Long operating periods (months!)

Basic Design

Sample Introduction

Sample Chemistry

Sample Detection

LLNL-PRES-406833


Columns!

To Sample Detection

LLNL-PRES-406833


System Components• Cheminert valves, PEEK material, micro-electric actuation• ISCO peristaltic pumps• Tubing – FEP – ID = 0.03” (0.762 mm)• Columns – FEP tubing, 10cm length

Volumes 0.762 mm tubing – 45.6 l 0.508 mm tubing – 20.3 l 0.254 mm tubing – 5.1 l

Frits PEEK, 0.5 or 2 Frit-In-A-Ferrule™

LLNL-PRES-406833


Slurry Pump

Waste

Sample Injection / Elution

Sample Detection Waste

Waste

Flush Pump

12 8

3 7

4 65

Col

1

2 10

3 9

4 8

5 7

6

1

2 4

3

1

2 4

3

12 8

3 7

4 65

Col

Both columns owned by the 10-port switching valve

Condition Pump

12 6

3 54

Slurry Reservoir

LLNL-PRES-406833


LLNL-PRES-406833


Sample Introduction• ICP style nebulizer• Frit collection• Accumulator Column

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Sample production and detection• Electrospray?

Rapid for very small volumes. Collection on mylar tape?

• Adsorption onto functionalized surfaces Rapid source prep. Equivalent to electroplated sources.

• Array of PIPS detectors for and SF.

LabVIEW control

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Why DGA?

10-2 10-1 100 10110-1

100

101

102

103

104

105

10-2 10-1 100 10110-1

100

101

102

103

104

105

Nb(V)

Pb(II)

Zr(IV)

Nb(V) Zr(IV) Bi(III) Pb(II)

k' for V(V), Ti(IV), Al(III),Fe(III), Co(II), Cu(II), Ni(II),

Zn(II) < 2 for all [HNO3]

k'

[HNO3]

Bi(III)

Cu(II)

Fe(III)

Bi(III)

k' for Ti(IV), Al(III),Co(II), Ni(II), Pb(II),

Zn(II) < 2 for all [HCl]

Bi(III) Fe(III) Cu(II)

[HCl]

LLNL-PRES-406833


Why DGA?

10-2 10-1 100 10110-1

100

101

102

103

104

105

106

10-2 10-1 100 101

TODGATRU

Am

U

Th

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

k'

[HNO3]

Pu

Am

U

Th

Pu

[HNO3]

LLNL-PRES-406833


What is DGA? – Eichrom technologies commercial product• N,N,N’,N’-tetra-n-octyldiglycolamide (DGA Resin, Normal)• N,N,N’,N’-tetrakis-2-éthylhexyldiglycolamide (DGA Resin, Branched)

LLNL-PRES-406833


Why Db?• Good range of t1/2 for study, seconds to 1 day (268Db, terminal nuclide

for the 288115 decay chain).• New chemical system for testing.• Chemistry is amenable to automation.• Provides testing platform for the automated chemistry system, to be

run either rapidly or slowly.

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Testing needs –• Ta, Hf, Pa, others?• Noted lack of F- (or other complexing agent) in the Eichrom data.

+5’s tend to form colloidal species without it• Method

Batch extraction studies 10 – 20 mg Normal DGA resin 1mL aqueous phase Agitate for at least 10 min, typically 1 hour Separate using 0.45m syringe filter -spec for detection

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Uptake on DGA, no HF

1.0E+00

1.0E+01

1.0E+02

1.0E+03

1.0E+04

1.0E+05

1.0E+06

0.1 1 10[HNO3]

K'

HfZrNbTa

LLNL-PRES-406833


Uptake on DGA, [HF] = 0.001M

1.E+00

1.E+01

1.E+02

1.E+03

1.E+04

1.E+05

1.E+06

0.1 1 10[HNO3]

K'

TaPaNpHfZrNb

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1.E-011.E+001.E+011.E+021.E+031.E+041.E+051.E+06

0.1 1 10[HNO3]

K'

TaPaNpHfZrNb

LLNL-PRES-406833



1.E-041.E-031.E-021.E-01

1.E+001.E+011.E+021.E+031.E+04

0.1 1 10[HNO3]

K'

TaPaNpHfZrNb

LLNL-PRES-406833


MS-4 Fractional Radionuclide Activity Distribution

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

SampleLoad

Strip 1 Strip 2-1

Strip 2-2

Strip 2-3

Strip 2-4

Strip 2-5

Strip 2-6

Strip 3

Experimental Fraction

Activ

ity Fr

actio

n

243Am 237Np 233Pa 182Ta (Avg)

Sample Loading: 0.4 M HNO3/ 0.02 M HF, 1 mLStrip 1 (Pa): 0.4 M HNO3/0.1 M HF, 5 mL

Strip 2 (Ta): 8M HNO3/0.1 M HF, 6 x 5 mLStrip 3: 0.1 M Ammonium Bioxalate, 5 mL

LLNL-PRES-406833


Next Steps• Kinetics Study – Getting started

Eu+3 data from Eichrom Not the case with +5’s

• Hf – Local production from 175Lu (p,n) 175Hf

automated radiochemistry efforts at llnl

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