1. Rapid Actinide Analysis for Large Soil Samples
Sherrod L. Maxwell, III
Westinghouse Savannah River Company

2. Background
Need for improved analysis of large soil samples for actinides
large sample size - lower detection limits
total dissolution-refractory actinides
minimize problems with column load solutions
removal of soil matrix interferences
consistency in tracer recoveries
good alpha peak resolution

3. Recent Work Using Actinide Resin (Dipex) and Diphonix Resin
Actinide Resin and Diphonex Resin
W.C. Burnett et al, "Preconcentration of Actinide Elements from Soils and Large Volume Water Samples Using Extraction Chromatography". Journal of Radioanalytical & Nuclear Chemistry. Vol. 226, (May 1997),
W.C. Burnett et al, Efficient Preconcentration and Separation of Actinide Elements from Large Soil and Sediment Samples, Analytical Chemistry, Vol. 72, pp (2000)
Diphonex Resin
S.L. Maxwell and S. Nichols, “Actinide Recovery Method for Large Soil Samples”, Radioactivity and Radiochemistry Journal (January, 2001)

4. Actinide Resin/Diphonix Resin-Soil
Eliminated soil matrix but still had some disadvantages:
Actinide Resin/Diphonix Resin (Burnett)
high phosphate -HEDPA solvent destruction (Fenton’s Reagent)- large TRU column
Fe in Fenton’s reagent -can’t stack TEVA+TRU cartridges
Diphonix (Maxwell)-requires microwave dissolution of resin
microwave work takes time/ can be tedious
using HEDPA strip instead of microwave on fecal samples
Pre-concentration steps take time and can have losses
Need a simple, user-friendly, effective approach

5. New Soil Method Cerium fluoride precipitation for soil matrix removal
CeF3 used for high iron water samples
M. Schultz et al, “Analysis of Am, Pu and Th in Large Volume Water Samples in the presence of High Concentrations of Iron”, International Radiochemical Analysis Conference, Maidstone, Kent, UK, Sept. 2002
Rapid elimination of soil matrix problems
Rare earth removal for large soil samples anyway-no extra separation time

6. Benefits Faster Total dissolution (5-10 grams)
After drying, blending, overnight furnace:
1 day sample preparation + 1 day column extraction
Previous method 4-5 days
Total dissolution (5-10 grams)
High recoveries/clean spectra
Eliminates interferences (Ex. Th, Po)
Th-228 on Pu-238, Am-241, etc
Po-210 affecting U-232

7. Soil Sample Preparation
Total dissolution and matrix removal (1 day)
After drying and blending, heat at 550C
Ash with nitric acid/HF to remove silicon, then fusion
Fusion in zirconium crucibles for 20 minutes at 700C
10 grams sodium peroxide + 5 grams sodium hydroxide (or as needed for larger samples)
Hydroxide precipitation
Iron carrier with TiCl3 reductant
Barium to eliminate carbonate interference
Additional Ce carrier sometimes added here for very sandy samples to enhance precipitation

8. Soil Sample Preparation, contd.
Redissolve in dilute HCl and perform cerium fluoride precipitation (1 mg to ~5 mg Ce) with TiCl3 present
Rinse precipitate with 0.25M HCl- 6MHF with 0.02M rongalite present
Soil load solution:
5 mLs 3M HNO3-0.25M boric acid
6 mL 7M HNO3
7.5 mL 2M AL(NO3)3

9. Transfer to crucible after silicon removal

10. 10 grams sodium peroxide + 5 grams sodium hydroxide
700C for 20 minutes

11. Just add water after cooling briefly

12. Dilute to 1 liter with water with iron
carrier, TiCl3, and barium present

13. After centrifuging, acidify
and add TiCl3, Ce and HF.

14. Place on ice, then centrifuge

15. Rinse with dilute HCl,
HF with rongalite present

16. Redissolve in acid, boric acid
and aluminum nitrate

17. TEVA +TRU Resin-Stacked Cartridges

18. 2.0mL TRU-Resin (3mL if needed) Cerium fluoride / Alpha spectrometry
Actinides in Soil
1) Redissolve in 18.5 mL 3M HN M Al(NO3) M boric acid
2) Add 0.5 mL 1.5M Sulfamic Acid mL 1.5M Ascorbic Acid
3) Add 1 mL 3 M Sodium Nitrite
Rinse
Beaker rinse: 3mL 5MHN03
Separate cartridges:
TEVA: 5 mL 3MHN03 Collect/acidify -
with 2 mL16M HN03 then to TRU
TEVA:10 mL5M HNO3
8 mL3M HN03
Th Elution
20mL 9MHCI
Pu (and/or Np) Elution
20mL
0.10MHCl MHF M TiCl3
Remove TRU cartridge:
1) Elute Am with 15mL 4M HCI
2) Add 3M HNO3 rinse from TEVA
3) 10 mL 6M HNO3 -remove any Po-210
4) 15 mL 4M HCl-0.2M HF-remove Th
5) Elute U with 15mL 0.1M ammonium
bioxalate
Add 0.5 mL 30 wt% H2O2
2mL TEVA Resin
( um)
Cerium fluoride
Alpha spectrometry
2.0mL TRU-Resin (3mL if needed)
( um)
Cerium fluoride / Alpha spectrometry

19. (warm and rinse original beaker)
Am/RE Removal on TEVA
1) Evaporate 4M HCl with 5mL con.HNO3, 50 uL of 1.8M H2SO4, then ash with nitric acid and hydrogen peroxide
2) Redissolve in 5 mL of 4M NH4SCN, warm gently.
Rinse
Beaker rinse: 3mL 4M NH4SCN, warm
10 mL 1.5 M NH4SCN to column
Am Elution
25 mL 1M HCl
(warm and rinse original beaker)
2mL TEVA Resin
( um)
Cerium fluoride
Alpha spectrometry

20. Final Am Clean-up on TEVA

24. QAP 0309-SOIL
SRS EML Ratio Pu Pu Am U U
Results in Bq/kg
5 gram sample analyzed

25. QAP 0403-SOIL
SRS EML Ratio Pu Pu Am U U
Results in Bq/kg
5 gram sample analyzed

28. Summary Large sample size Total dissolution
fast fusion, multiple samples
Removal of soil matrix interferences
Cerium fluoride precipitation
Reduced sample preparation time by 2 days
Good tracer recoveries and alpha peak resolution
Reduced spectral interferences