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

Automated Radiochemistry Efforts at LLNL

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 Directorate Lawrence Livermore National Laboratory *University of Nevada-Las Vegas

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

Lawrence Livermore National Laboratory, P.O. Box 808, Livermore, CA 94551 LLNL-PRES-406833

Automated Radiochemistry Efforts at LLNL

   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

Automated Radiochemistry Efforts at LLNL To Sample Detection Columns!

LLNL-PRES-406833

Automated Radiochemistry Efforts at LLNL

 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 m l 0.508 mm tubing – 20.3 m l  0.254 mm tubing – 5.1 m l  Frits  PEEK, 0.5 m or 2 m Frit-In-A-Ferrule ™ LLNL-PRES-406833

Automated Radiochemistry Efforts at LLNL

Slurry Reservoir Sample Injection / Elution 2 1 6 3 4 5 Slurry Pump Condition Pump Flush Pump Waste 2 1 3 4 2 1 8 4 5 6 Sample Detection 3 2 1 10 9 4 5 8 6 7 2 1 3 4 Waste 2 1 8 4 5 6 LLNL-PRES-406833 Waste Both columns owned by the 10-port switching valve

Automated Radiochemistry Efforts at LLNL

LLNL-PRES-406833

Automated Radiochemistry Efforts at LLNL

 Sample Introduction • ICP style nebulizer • • Frit collection Accumulator Column LLNL-PRES-406833

Automated Radiochemistry Efforts at LLNL

 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 a and SF.

 LabVIEW control LLNL-PRES-406833

Automated Radiochemistry Efforts at LLNL

 Why DGA?

10 10 4 10 3 5 Nb(V) Zr(IV) Bi(III) Pb(II) Bi(III) Zr(IV) 10 10 10 5 4 3 Bi(III) Fe(III) Cu(II) Bi(III) k' 10 10 2 1 Nb(V) Pb(II) 10 0 10 -1 10 -2 k' for V(V), Ti(IV), Al(III),

Fe(III)

, Co(II), Cu(II), Ni(II), Zn(II) < 2 for all [HNO 3 ] 10 -1 [HNO 3 ] 10 0 10 2 10 1 k' for Ti(IV), Al(III), Co(II), Ni(II), Pb(II), Zn(II) < 2 for all [HCl] 10 0 Fe(III) Cu(II) 10 1 10 -1 10 -2 10 -1 [HCl] 10 0 LLNL-PRES-406833 10 1

Automated Radiochemistry Efforts at LLNL

TRU  Why DGA?

10 6 Pu 10 5 Th 10 4 U 10 3 k' 10 2 Am Th Am Pu TODGA 10 1 U 10 0 Pu(IV) Th(IV) U(VI) Am(III) 10 -1 10 -2 10 -1 10 0 [HNO 3 ] 10 1 10 -2 10 -1 10 0 [HNO 3 ] 10 LLNL-PRES-406833 1

Automated Radiochemistry Efforts at LLNL

 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

Automated Radiochemistry Efforts at LLNL

 Why Db?

• Good range of t 1/2 for study, seconds to 1 day ( for the 288 115 decay chain).

268 Db, terminal nuclide • • • 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.

LLNL-PRES-406833

Automated Radiochemistry Efforts at LLNL

 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 0.45

g -spec for detection m m syringe filter LLNL-PRES-406833

Automated Radiochemistry Efforts at LLNL

Uptake on DGA, no HF 1.0E+06 1.0E+05 1.0E+04 1.0E+03 1.0E+02 1.0E+01 1.0E+00 0.1

1 [HNO 3 ] 10 LLNL-PRES-406833 Hf Zr Nb Ta

Automated Radiochemistry Efforts at LLNL

Uptake on DGA, [HF] = 0.001M

1.E+06 1.E+05 1.E+04 1.E+03 1.E+02 1.E+01 1.E+00 0.1

1 [HNO 3 ] 10 LLNL-PRES-406833 Ta Pa Np Hf Zr Nb

Automated Radiochemistry Efforts at LLNL

Uptake on DGA, [HF] = 0.02M

1.E+06 1.E+05 1.E+04 1.E+03 1.E+02 1.E+01 1.E+00 1.E-01 0.1

1 [HNO 3 ] 10 LLNL-PRES-406833 Ta Pa Np Hf Zr Nb

Automated Radiochemistry Efforts at LLNL

Uptake on DGA, [HF] = 0.1M

1.E+04 1.E+03 1.E+02 1.E+01 1.E+00 1.E-01 1.E-02 1.E-03 1.E-04 0.1

1 [HNO 3 ] 10 LLNL-PRES-406833 Ta Pa Np Hf Zr Nb

Automated Radiochemistry Efforts at LLNL MS-4 Fractional Radionuclide Activity Distribution

1 0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0 Sample Load Strip 1 Strip 2 1 Strip 2 2 Strip 2 3 Strip 2 4 Strip 2 5 Experimental Fraction Strip 2 6 243Am 237Np 233Pa 182Ta (Avg) Strip 3

Sample Loading:

0.4 M HNO 3 / 0.02 M HF, 1 mL

Strip 1 (Pa):

0.4 M HNO 3 /0.1 M HF, 5 mL

Strip 2 (Ta):

8M HNO 3 /0.1 M HF, 6 x 5 mL

Strip 3:

0.1 M Ammonium Bioxalate, 5 mL LLNL-PRES-406833

Automated Radiochemistry Efforts at LLNL

 Next Steps • • Kinetics Study   Eu +3 – Getting started data from Eichrom Not the case with +5’s Hf – Local production from 175 Lu (p,n) 175 Hf LLNL-PRES-406833