analysis of actinide elements from large environmental samples guebuem kim bill burnett florida...
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Analysis of Actinide Elements from Large Environmental Samples
Guebuem KimBill Burnett
Florida State Universityand
E. Philip HorwitzPG Research Foundation, Inc.
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Need for Large Volumes
Achieve low MDA's for environmental monitoring
Specialized scientific studies often require large volumes to obtain necessary sensitivity, e.g., Am/Pu in seawater, global fallout in recent soils
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Analytical Challenges
Preconcentration of actinides from natural water samples may require handling up to 100-400 liters
Large (5-10 grams or more) soil/sediment samples may require difficult and lengthy dissolution procedures
Separation chemistry, especially from large soil/sediment samples, suffers from “matrix effects.”
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Actinides in Natural Waters
PrecipitateMnO2
Sepa
rati
on
Am, Pu, etc.• alpha spectrometry• ICP-MS
10's - 100's liters+ tracers
pH = 2KMnO4
NaOH, pH = 8MnCl2
Resins:• UTEVA• TRU
2M HCl/NH2OH.HCl50 mg FeNaNO2
pH = 6-7
PrecipitateFe(OH)3
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Marine Environment LaboratoryMonaco
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Am/Pu from 200-L Seawater
Supernatant seawater transferred from one plastic tank to another via pumping — this
will be used for 90Sr and 137Cs.
MnO2 suspension withdrawn from bottom of conical-shaped
plastic tanks — processed for Am and Pu.
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Irish Sea Water Results
P ara m e t er
IAEA
R ec omm e nd e d
Va lu e
mBq/kg
IAEA
Con f id e n ce
I nt er v a l
mBq/kg
M EL /FS U
R e sult
mBq/kg
M EL /FS U
Y i e ld
%
239,240P u 13.2 12.4 - 14.0 14.1±0.8 99.0
238P u 3.16 2.80 - 3.82 3.0±0.2 99.0
241Am 16.0 8.40 - 20.0 17.0±1.1 95.0
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Soils and Sediments
Dissolution/Leaching
Dip
honi
xoxidation
Resins:• TRU• TEVA• UTEVA
tracersFe(OH)3 ppt0.1M HCl-0.3M HF, AA
"Matrix"
0.5M HEDPA
H3PO4
{oneor
more
Sepa
rati
on Am, Pu, etc.• alpha spectrometry• ICP-MS
• Ozonation• “Fenton’s Reagent”
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DiphonixIon Exchange Resin
Features of Diphonix:• diphosphonic & sulfonic acid groups• polystyrene/divinylbenzene matrix• extremely high actinide retention,
low common ion adsorption• tolerant to HF
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Actinide Retention on Diphonix Resin
Diphonix Resin shows high
retention for all Actinides
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Adsorption of 241Am
HCl (Molarity)
10-2 10-1 100 10150
60
70
80
90
100
Adsorption of actinides highest at pH ~1-2
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HEDPA
1-hydroxyethane-1, 1-diphosphonic acid
Molecular weight = 206.03Elution sequence: Th(IV) = Pu(IV) >
U(VI) > Am(III)Reagent-grade expensive (Fluka: 50 g
~ $165) — option to purify industrial grade (Albright & Wilson: “BRIQUEST” ADPA-60AW U)
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Elution:HEDPA
Acid Dependency
Curves
Indicates that actinides should
elute easily at concentrations
~0.5M
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Elution of Am
0.5M HEDPA Elution Volume (mL)
0 5 10 15 20 25 30 35 400
20
40
60
80
100
Prior ResultIncremental
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HEDPA Destruction via Ozone
0%
20%
40%
60%
80%
100%
120%
50 70 90 110 130 150 170
Time (min)
20-mL elution was diluted to 70 mL, H2O2 added (0.5M), pH adjusted to 9.0 with NaOH, and samples
ozonated for variable lengths of time
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Ozonation Process
Ozone delivered from an ozone generator via a gas diffusion stone oxidizes the HEDPA
sample
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Oxidation by Fenton’s Reagent
finished
Treatment:
40 mL 0.5M HEDPA + 1 mL
HNO3 + 40 mL H2O2 + 0.17 g
Fe(NH4)2(SO4)26H2O
Temperature ~90oC
H2O2 + Fe2+ OH + OH- +Fe3+
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Actinide Separations
TRUTRU
Resin
12
3 45
6
3
2
12.5M HNO3
2.5M HNO3/0.1M NaNO2
2.5M HNO3
9M HCl4M HCl
4M HCl/TiCl3 6
5
4
4M HCl2.5M HNO3
2.5M HNO3/0.1M NaNO2
2.5M HNO3
9M HCl1M HCl
0.1M Ammonium Bioxalate
12
3 45
6DiscardAm
Pu DiscardTh
U
Sample(3M HNO3, 0.7M Al(NO3)3, FS, AA)
Final clean-ups: Am/Ln on TEVA; U on UTEVA
TRUResin tolerates high PO4
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Sensitivity to PO4
UTEVA.Resin TRU.Resin
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Preliminary Tests
50 60 70 80 90 100
TRU.Resin
HEDPA Destruction
HEDPA Elution
Diphonix Adsorption
Fe(OH)3 ppt
Yield (%)
AmTh
Am-241 and Th-234 spiked samples. Matrix = HNO3/HCl leach of 10-g NIST Rocky Flats II soil
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Standard Samples: Yields
Am Pu Th U50
60
70
80
90
100
Samples (n=7):•3 EML soils•2 IAEA sediments•2 Fe-rich soils
5 intercomparison samples and 2 Fe-rich samples run through entire procedure and analyzed for Am, Pu, U, and Th. 10-gram
samples were leached with HNO3/HCl.
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Standard Samples: Results
0.60 0.70 0.80 0.90 1.00 1.10
EML-9409
EML-9509
EML-9803
IAEA-300
IAEA-135
Activity Ratio: FSU/Standard
Am-241 Pu-239/240
Table 1: EML and IAEA intercomparison values.
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Summary
Uptake of actinides onto Diphonix from complex matrices is very efficient
0.5M HEDPA easily elutes actinides“Fenton’s Reagent” or O3 successfully
oxidizes HEDPASeparations starting with TRUResin
prevent PO4 interference