Rapid Determination of Actinides
in Urine by ICP-MS + Alpha Spec.

AN-1437
Summary of Method Actinides are separated and concentrated from 100mL urine samples. Actinides areconcentrated from urine samples using a calcium phosphate precipitation. Pu, Np, Am-Cm, and U are separated on 2mL
cartridges of Eichrom TEVA, TRU and DGA resins. Pu-Np are measured by ICP-MS. Measured values for 239Pu and237Np agreed to within 1-2% of reference values, while 241Am and 244Cm agreed to within 2-3%. Decontamination factorsof >106 were achieved for Pu over U (238U-H can interfere with the measurement of 239Pu by ICP-MS). Sample
preparation for batches of 12 samples can be completed by a single operator in <8 hours.
Reagents
TEVA Resin, 2mL Cartridges (Eichrom TE-R50-S)
TRU Resin, 2mL Cartridges (Eichrom TR-R50-S)
DGA Resin, Normal, 2mL Cartridges (Eichrom DN-R50-S)
Iron carrier (50mg/mL Fe, as ferric iron nitrate)
242Pu (ICP-MS) or 236Pu (alpha) tracer
233U (ICP-MS) or U232 (alpha) tracer
243Am tracer
Ce carrier (1mg/mL)
1.25M Ca(NO3)2
3.2M (NH4)2HPO4Deionized Water
2M Al(NO3)3
HNO3 (70%)
HCl (37%)
NH4OH
HF (49%) or NaF
NaNO2Denatured ethanol
Sulfamic Acid
Ascorbic Acid
Oxalic acid/Ammonium oxalate
Hydroxylamine Hydrochloride
Equipment
Vacuum Box (Eichrom AR-24-BOX or AR-12-BOX)
Cartridge Reservoir, 20mL (Eichrom AR-200-RV20)
Inner Support Tubes-PE (Eichrom AR-1000-TUBE-PE)
Yellow Outer Tips (Eichrom AR-1000-OT)
Resolve Filters in Funnel (Eichrom RF-DF25-25PP01)
600mL Glass beakers
Stainless Steel Planchets with adhesive tape
Alpha Spectrometry System
ICP-MS System
50mL and 250mL Centrifuge Tubes
Centrifuge
Heat Lamp
Hot Plate
Analytical Balance
Vacuum Pump

Figure 1. Sample Preparation
Urine Sample + Tracers
Add 1mL 1.25M Ca(NO3)2 and3mL 3.2M (NH4)2HPO4. Mix well.
Heating to near boiling can improve
tracer/analyte equilibration.

Adjust to pH 9 with NH4OH.
Cool to room temperature.
Centrifuge 3500 rpm, 5 min.
Decant Supernate.
Dissolve precipitate in 8mL 6M HNO3
and 8mL 2M Al(NO3)3.
Cool samples to room temp.
Fix valence by adding: (mix between steps)-0.5mL 1.5M sulfamic acid
-40uL 50mg/mL Fe carrier-1.5mL 1M ascorbic acid (Wait 3 min)
-1mL 3.5M NaNO2

Figure 2. Actinide Separation on TEVA - DGA(1) Precondition 2mL TEVA+TRU
with 10mL 6M HNO3.
(2) Load Sample.
TEVA(3) Rinse centrifuge tube with
5mL 6M HNO3. Add to TEVATRU.*
TRU(4) Rinse TEVA+TRU with
5mL 3M HNO3.
(5) Separate TEVA and TRU.
(6) Rinse TEVA with:-30mL 3M HNO3
-15mL 9M HCl (Th removal)(7) Add DGA below TEVA.**(8) Strip Pu/Np from TEVA to
DGA with 15mL 3M HNO30.1M Ascorbic acid-0.02M
Fe2+.
(9) Separate TEVA and DGA.

TEVA

DGA

(10) Rinse TEVA with 5mL 3M HNO3.
(11) Strip Np from TEVA with 14mL
0.25M HCl-0.005M HF-0.01M
Hydroxylamine hydrochloride.

(12) Rinse DGA with:-5mL 8M HNO3
-20mL 0.1M HNO3
-10mL 0.05M HNO3.

(20) Wet filter with 3mL 80% ethanol
followed by 3mL DI water.

(13) Strip Pu from DGA with 11mL
0.02M HCl-0.005M HF-0.01M
Hydroxylamine hydrochloride.
(14) Strip Am/Cm from TRU with
15mL 4M HCl.
(15) Rinse TRU resin with 15mL
4M HCl-0.2MHF.

(21) Filter sample.
(22) Rinse sample
tube with 5mL
DI water andadd to filter.
(23) Rinse filter funnel
with 3mL DI water.
(24) Rinse filter funnel
with 2mL 100% ethanol.

(25) Draw vacuum until filter is dry.
(26) Remove filter from funnel
assembly and mount filter on(17) Measure Np, Pu and U by ICP-MS.
stainless steel planchet with(18) Add 50ug Ce carrier and 0.5mL
adhesive tape.
30% H2O2 to each Am-Cm sample.
(27) Dry filter under heat lamp forMix well. Add 1mL 49% HF. Mix
3-5 minutes.
well. Wait 15-20 min.
(28) Measure actinides by alpha
spectrometry.
(19) Set up Resolve® Filter Funnel(16) Strip U from TRU with 15mL
0.01M ammonium bioxalate.

on vacuum box.

* Adding 50uL of 30% H2O2 to the 6M HNO3 tube rinse can help improve U recoveries and decontamination in the Np and
Pu fractions.
** Adding a 1mL UTEVA cartridge between TEVA and DGA can help improve uranium decontamination.

References
1) Sherrod L. Maxwell, Vernon D. Jones, “Rapid determination of Actinides in urine by ICP-MS and alpha
spectrometry: A hybrid approach,” Talanta, 80(1), 143-150 (2009).
2) Sherrod L. Maxwell, Brian K. Culligan, Vernon D. Jones, Sheldon T. Nichols, Gary W. Noyes, Maureen A. Bernard,“Rapid Determination of 237Np and Plutonium Isotopes by ICP-MS and Alpha Spectrometry,” Health Physics,
101(2), 180-186 (2011).
1955 University Lane Lisle, IL 60532, USA+1 (630)963-0320

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