Rapid Separationsfor Environmental Level and Highfor Environmental Level and High

Activity Radioactive Solutions

Lawrence JassinEichrom Technologies LLC

March 3, 2008Pittcon 2008

N O l LANew Orleans, LA

OutlineOutline

• Introduction to Extraction ChromatographyIntroduction to Extraction Chromatography• Three Separation Applications

A ti id i L S il S l– Actinides in Large Soil Samples• Work by Sherrod Maxwell, Savannah River Site

Se 79 in Savannah Rive Tank Waste– Se-79 in Savannah Rive Tank Waste• Work by Dave and Cecilia DiPrete, SRNL

Tc 99 Separation in a Spent Nuclear Fuel– Tc-99 Separation in a Spent Nuclear Fuel Reprocessing System

• Work by Phil Horwitz and Dan McAlister PGRFWork by Phil Horwitz and Dan McAlister, PGRF and Gordon Jarvinen, LANL

Extraction Chromatography

Solvent Extraction Column Chromatographyg p y

Extraction Chromatographic ResinExtraction Chromatographic Resin

Inert support =

M A liMacroporous Acrylic Resin

Example Stationary Phases = CMPO, ,

quaternary and tertiary amines, diglycolamide

Extractants

N

O

ON

O

C8H17 C8H17P

OO

C8H17 N N NC8H17

C8H17 C8H17

N

CMPO (TRU and RE Resin)

Tetraoctyldiglycoloamide (DGA Resin, Normal)

Am3+ + 3X- + 3E ↔ AmX3E3X = Cl- or NO3-

k'A as a Function of HNO3 and HCl

4

105

4

105k Am as a Function of HNO3 and HCl

DGA

103

104

103

104

102 102 k' Am(III)

DGA

101 101Am(III)

TRU

10-1

100

10-1

100TRU

10-2 10-1 100 10110

10-2 10-1 100 10110

[HNO3] [HCl]

Actinides in Soil MethodsActinides in Soil Methods

5 10 il th d• 5-10 g soil method– Lower MDA than typical 1 gram methods– Rugged even for refractory soil– NaOH Fusion/cerium fluoride precipitation

(TEVA TRU DGA i )(TEVA+TRU+DGA resins)– Pu, Np, Am, Cm, U, Th

“Rapid Column Extraction Method for Actinides in Soil”, Journal of Radioanalytical and Nuclear Chemistry, Vol. 270, No. 3 (December, 2006)( )

Need to Analyze Larger Sample AliquotsNeed to Analyze Larger Sample Aliquots

Actinides in Soil MethodsActinides in Soil Methods• 100-200g soil methodg

– Pu and Am/Cm– Cerium fluoride matrix removal / select against

Uranium– TEVA+TRU+DGA resins

High recoveries (Pu Am 80 90% for 200 g samples)– High recoveries (Pu, Am 80-90% for 200 g samples)– Very low MDA - 3E-5 pCi/g (0.001 Bq/kg)-16 hour

count

Rapid Method for Determination of Plutonium, Americium and Curium in Large Soil Samples, Journal of Radioanalytical and Nuclear Chemistry, Vol. 275, No. 2(2007)

. Add Tracers (Pu242 or Pu236, Am243).

Heat to 550C

100-200g Soil Method

Acid leach (75-100 mL con. HNO3 + 25 mL HCl). Heat todryness on hot plate. Rinse with con. HNO3, 4M HCl.

Centrifuge, Filter, Evaporate. Ash with con. HNO3.

Fuse in Zr Crucible 20 min. (20-25 g NaOH - 600C).Hydroxide precipitation (7 mg Ce carrier, TiCl3, Ba).

Cerium Fluoride matrix removal (2 mg Ce HCl/HF H2O2)Cerium Fluoride matrix removal (2 mg Ce, HCl/HF, H2O2)

Redissolve in 5 mL 3M HNO3-0.25M Boric Acid, 6 mL 7MHNO3, 7.5 mL 2M Al(NO3)3.

Add 0.5 mL 1.5M Sulfamic Acid and 1.25 mL 1.5MAscorbic Acid. Add 1 mL 3.5M NaNO2.

Load to TEVA + TRU + DGA Resin (2 mL cartridges).Add 3 mL 6M HNO3 beaker rinse. Split Cartridges.

DGARinse with 5 mL 0.25M HNO3

(Remove U)

TEVARinse with 10 mL 5M HNO3

10 mL 3M HNO323 L 9M HCl (R Th) (Remove U)23 mL 9M HCl, (Remove Th)

5mL 3M HNO3 rinse TEVA.Elute with 20 mL 0.1M HCl-0.05M HF

- 0.03M TiCl3

Stack TRU + DGAAdd 15 mL 4M HCl

(Move all Am/Cm to DGA).

Add 0.5 mL 30 wt% H2O2to oxidize any U.

Add 50 ug Ce + 1 mL 49% HF. Filter. Count by alpha spectrometry

DGAAdd 10 mL 0.25M HCl (Elute Am-Cm)

Evaporate with con. HNO3 and 50 uL of10% sulfuric acid.

Ash once with 3 mL con. HNO3 and2 mL 30 wt% H2O2

Redissolve in 5 mL 4M NH4SCN-0.1M Formic Acid. Load to TEVA.

Rinse beaker with 3 mL 4M NH4SCN-0.1M Formic Acid.Rinse TEVA with 10 mL 1.5M NH4SCN-0.1M Formic Acid.

Elute Am-Cm with 25 mL 1M HCl.Add 50 ug Ce + 2 mL 49% HF.

Filter. Count by alpha spectrometry.

Matrix Removal using Cerium FluorideMatrix Removal using Cerium Fluoride

Cerium Fluoride Precipitate

Column load solution

TEVA+TRU+DGA Resins For Soils

Soil (5-10 g)-fusion/CeF3 ppt

Soil (200 g)-leach/CeF3 ppt

TEVA (Pu, Np,Th)

TRU (U)

DGA (Am Cm)DGA (Am, Cm)

MAPEP MAS-15 PerformanceMAPEP MAS 15 Performance

SRS REF. Ratio

Pu-238 56.9 61.15 0.93Pu-239 41 0 45 85 0 89Pu-239 41.0 45.85 0.89Am-241 51.1 57.08 0.90U-234 35.6 37.00 0.95U 238 38 9 38 85 1 00U-238 38.9 38.85 1.00

Results in Bq/kgq g5 gram sample analyzedMAPEP=DOE Mixed Analyte Performance Evaluation

program standardp g

100 g Samples with MAPEP-05-S14 Soil Standard Added100 g Samples with MAPEP 05 S14 Soil Standard Added

Soil Sample Pu-242 Pu-238 Am-243 Am-241Tracer Measured/ Tracer Measured/Recovery Reference Recovery Reference

100g + 1 g S14 77.2 % 0.99 90.0% 0.95100g + 3 g S14 91.5% 0.97 97.5% 0.87100g + 3 g S14 88.2% 0.95 95.3% 0.86

Avg. 85.6% 0.97 94.3% 0.90

Unspiked sample=0.120 Pu-238 Bq/kg and 0.152 Am-241 Bq/kg

0.0608 Bq Pu-238 and 0.0811 Bq Am-241 added per 1 gram of S14

200 g Samples with MAPEP-05-S14 Soil200 g Samples with MAPEP 05 S14 Soil Standard Added

Soil Sample Pu-242 Pu-238 Am-243 Am-241Tracer Measured/ Tracer Measured/Recovery Reference Recovery Reference

200g + 3 g S14 82.1 % 1.00 96.6% 0.80

200g + 3 g S14 81 4% 1 04 90 0% 0 82200g + 3 g S14 81.4% 1.04 90.0% 0.82

Avg. 81.8% 1.02 93.3% 0.81

Unspiked sample=0.120 Pu-238 Bq/kg and 0.152 Am-241 Bq/kg

0.0608 Bq Pu-238 and 0.0811 Bq Am-241 added per 1 gram of S14

Challenges of SRS Se-79 Measurements in SRS High Activity Samples

Select Fission Product Distributions Over Time1 0E+00

1.0E-02

1.0E-01

1.0E+00iv

ity

Cs-137Sr-90/Y-90

Sm-151

Sb 12

1.0E-04

1.0E-03

ion

of R

adio

acti

Tc-99

Sb-125

1.0E-06

1.0E-05Frac

t

Sn-126

Se-79 I 1291.0E-071.0E+01 1.0E+02 1.0E+03 1.0E+04

Age of Waste in Years

Se 79 I-129

Waste Acceptance Criteria requirements of various repositories often call for low level Se-79 measurements in the presence of high levels of interfering beta species.

Activities of Various Isotopes Separated from Se-79 in Waste Tank SampleSample

Se-79 Activities vs Activities of Some Other Radionuclides Present in SRS Waste TankWaste Tank

1.00E+06

1.00E+07

1.00E+04

1.00E+05

1.00E 06

PM/m

l)

#1

1.00E+02

1.00E+03

Act

ivity

(DP #1

#2#3

1.00E+00

1.00E+01

S C E A H P C S Y T SSb-125Cs-137Eu-154Am-241H-3

Pu-238Cm-244Sr-90

Y-90

Total BetaSe-79

Poor DF for Sb-125 with 30% TBP method

2 keV 30 k V 160 keV 500 keV2 keV 30 keV 160 keV 500 keV

Separation of Sb from SeSeparation of Sb from Se

• Sb quantitatively extracted in 6M HCl bySb quantitatively extracted in 6M HCl by RE resin, Se not extracted at all (Chloride system)system)

• Added to beginning of TBP Se procedure

New Se-79 ExtractionNew Se 79 Extraction• Sample aliquot spiked with Se carrier, acidified to 6M

HClHCl• Added to 2 mL RE Resin cartridge, eluate diluted with DI

water to 1M HCl• Se metal precipitated with Titanous Chloride and

Hydroxylamine Hydrochloride, precipitate filtered, rinsedR di l d i 9 M HB• Re-dissolved in 9 M HBr

• Se extracted with 30% TBP, Se eluted with DI water• Aliquots analyzed by LSC for Se 79 and Se carrier by• Aliquots analyzed by LSC for Se-79 and Se carrier by

NAA

Se-79 Spectrum of Sample Run ThroughSe-79 Spectrum of Sample Run Through New Procedure

160 keV

Weak Base EC ResinWeak Base EC Resin

• Flow Sheet Development for GNEPFlow Sheet Development for GNEP– Conventional cross-linked macroporous resin

removes100 ppm Tc-99 well from 0 01M nitricremoves100 ppm Tc 99 well from 0.01M nitric acid containing 50-100 g/L Uranium

– Elution efficiency is not great with NH4OHElution efficiency is not great with NH4OH• Phil Horwitz suggests an Extraction

Chromatographic variation of the anionChromatographic variation of the anion resin

105100-150 um, 22(1)oC, 1 hr equilibration

k' on Weak Base EC Resin

10550-100 um, 22(1)oC, 1 hr equilibration

k' on Weak Base EC Resin

104Pu(IV)

Tc(VII)

104

10

Tc(VII)

103Np(IV)

Pu(IV)

103

h( )

102Th(IV)

k' 102U(VI)

Th(IV)

k'

101 101

Np(IV)

1

100

k' U(VI) < 2 for 0.05 - 2.0 M HNO3

100

Pu(IV)

10-2 10-1 100 10110-1 3

[HNO3], Μ10-1 100 101

10-1

[HCl], Μ

2 L l 100 150 22(1)oC fl t 2 L/ i Elution of

99Tc and 233U on Weak Base EC Resin

5

106

Rinse 0 1 M

99TcStrip1.0 M

2 mL column, 100-150 µm, 22(1) C, flowrate 2 mL/min

Load 10 mL of 0.1 MHNO3 +

99Tc or 233U

104

105 0.1 M HNO3

Tc233U1.0 M

NH4OH

103

104

pm/m

L

102

1096% Tc

ConclusionsConclusions

• Extraction Chromatographic Resins are aExtraction Chromatographic Resins are a flexible separation tool for…

Achieving ultra low detection levels– Achieving ultra-low detection levels– Cleaning up high activity waste

High value process separations– High value process separations• Application areas continue to grow…

– Radiopharmaceuticals– Emergency Response Methods