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
