1. Recent Improvements in Rapid Column Separation Methods at SRS
S. L. Maxwell, III, D. J. Fauth, R. C. Henderson, J. J. Smiley, S. R. Johnson
Westinghouse Savannah River Site

2. Recent Improvements SRS Environmental Monitoring lab SRS Bioassay lab
faster water and air filter analysis for actinides
improved soil-fecal sludge analyses (wastewater treatment plant samples)
SRS Bioassay lab
improved Pu-Np column extraction for urine (better Pu stripping/less volume)
faster fecal analysis method (no microwave)
Central Laboratory (process lab)
improved Pu, Np in HEU and LEU samples
TEVA + Pu-236 tracer

3. SRS Environmental Monitoring Lab
Vacuum box systems and stacked cartridges
Significant cost and time savings vs. gravity flow
Tested both stacked UTEVA+ TRU and TEVA+TRU methods
both methods work very well; much faster than gravity flow
eliminated evaporation of Am fraction: use 5 mL con HF
use 50 ug cerium instead of 100 ug to improve peak resolution

4. SRS Environmental Monitoring Lab
Showed stacked TEVA+TRU can be used on water samples
just like urine method- no iron interference
may have some advantages for air filters (Po-210 interference)
Po-210 can interfere with U-232 on UTEVA
allows Pu AND Np together on TEVA
use Ti (III) reductant in Pu strip from TEVA when performing cerium fluoride microprecipitation

5. Pu, Np/Am, U, Sr on TEVA/TRU RESIN (Water/Air filters)
1) Redissolve in 10 mL 3M HN M Al(NO3)3
2) Add 0.5 mL 1.5M Sulfamic Acid + 1 mL 1.5M Ascorbic Acid
3) Add 1 mL 3.5M Sodium Nitrite
Th Removal
3mL 9M HCI/25mL
8MHCI
Rinse
20 mL 3M HN03
Pu Elution
20mL
0.10M HCl MHF M TiCl3
Add 0.5 mL 3M sodium nitrite
2mL TEVA Resin
( um)
Cerium fluoride
Alpha spectrometry
Remove TRU cartridge:
1) Elute Am with
15mL 4M HCI
2) Elute U with
10mL 0.1M ammonium
bioxalate
2.0mL TRU-Resin
( um)
Collect, evaporate, dissolve in 6M HNO3
Sr Resin

6. Pu-242 Tracer Recoveries
1000 mL water samples/ Pu-242 tracer= 4.40 dpm
Calcium phosphate precipitation
% Pu242 Recovery % Pu242 Recovery
UTEVA+TRU Method TEVA+TRU Method
1) ) 99.3
2) ) 105
3) ) 105
4) ) 109
5) 98.6
6) 102
Avg. = 105% Avg. = 103% (

9. Am-243 Tracer Recoveries
1000 mL water samples/ Am-243 tracer= 3.84 dpm
Calcium phosphate precipitation
% Am-243 Recovery % Am-243 Recovery
UTEVA+TRU Method TEVA+TRU Method
1) ) 98.4
2) ) 99.0
3) ) 107
4) ) 100
5) ) 106
6) ) 105
Avg. = 101% Avg. = 103% (

12. U-232 Tracer Recoveries 1000 mL water samples/ U-232 tracer= 5.45 dpm
Calcium phosphate precipitation
% U-232 Recovery % U-232 Recovery
UTEVA+TRU Method TEVA+TRU Method
1) ) 87.5
2) ) 93.5
3) ) 97.4
4) ) 92.4
5) ) 94.0
6) 93.2
Avg. = 94.5% Avg. = 93.0% ( 3.8

13. SRS Environmental Monitoring Lab
Actinides in soil-fecal samples
dissolution and column flow problems with current method
need total dissolution/eliminate flow problems & low uranium
use Diphonix resin technology as in bioassay lab
Initial testing encouraging
Use sodium peroxide/sodium hydroxide fusion (Zr crucibles)
Precipitate actinides as hydroxides; redissolve in HCL-HF/also boric acid fraction
4 mLs Diphonix Resin + small volume HEDPA strip (15-20 mLs)
Faster HEDPA destruction method (no microwave)
modified Fenton’s Reagent method
Routine size Eichrom columns

14. Diphonix Stripping-HEDPA
0.5M HEDPA % Pu % U232
Strip Volume Tracer Tracer
1) 3 mL resin 15 mL
2) 4 mL resin 15 mL
3) 4 mL resin 20 mL
4) Direct -HEDPA 20 mL
Avg= % 98 %
Redissolve in 10 mLs 6M HNO3 and 10 mls 2.5M aluminum nitrate (to avoid
phosphate interference), then TEVA+ TRU Column extraction

15. Soil-Fecal Sludge Samples
Pu Pu Pu-239/240
% Recovery pCi/g pCi/g
1) 101%
2) 69 %
3) 84%
4) 49 %
Avg= 76%

16. Soil-Fecal Sludge Samples
U U U-235 U-238
% Recovery pCi/g pCi/g pCi/g
1) 56%
2) 75 %
3) 74%
4) 98 %
Avg= 76%

17. Soil-Fecal Sludge Samples
Am Am Cm-244
% Recovery pCi/g pCi/g
1) 73%
2) 53 %
3) 64%
4) 38 %
Avg=57%

18. Bioassay Lab Improvements
Actinides and Sr-90 in urine
stacked TEVA+TRU Resin cartridges with vacuum boxes
Pu-236 tracer for Pu and Np at same time
Pu, Np (TEVA) and U, Am (TRU)
Sr (Sr Resin)
Pu stripping improvement:
improved Pu stripping with rongalite instead of iodide in strip solution (less volume/faster flow rate)
rongalite (sodium formaldehyde sulfoxylate)
compatible with electroplating
adjust bisulfate added for sulfate added from rongalite decomposition (2.5 mLs 10 % bisulfate instead of 3 mLs)

19. Urine Batch: Calcium Phosphate Precipitation

20. Pu, Np/Am, U, Sr on TEVA/TRU RESIN (URINE)
1) Redissolve in 12 mLs of 3M HN03 - 1M Al(NO3)3
2) Add 0.5 mL 1.5M Sulfamic Acid + 2 mls 1.5M Ascorbic Acid
3) Add 2 mLs 4M Sodium Nitrite
Th Removal
5mL 9M HCI/
25mL 8M HCI
Rinse
20 mL 3MHN03
Pu Elution
20mL
0.10M HCl M HF M Rongalite
4mls 0.02M H2SO4 + 3mls 16M HN03
2mL TEVA Resin
( um)
Evaporate/ash
Electrodeposition
Remove TRU cartridge:
1) Elute Am with
15mL 4M HCI
2) Elute U with
20mL 0.1M ammonium
bioxalate
2.0mL TRU-Resin
( um)
Collect, evaporate, dissolve in 6M HNO3
Sr Resin

21. TEVA+ TRU Stacked Column: Pu, Np, U, Am

22. TRU Cartridge: U, Am Stripping

23. SR Cartridge: Sr-90 Separation

26. Pu-236 Recoveries-Urine Using TEVA/Rongalite
Pu-236=0.426 dpm
500 mL urine
Avg Recovery=99%

27. Spiked Urine Samples: Rongalite Test
Known values: Avg. measured:
Pu-238 =0.110 dpm/L Pu-238 =0.143 dpm/L
Pu-239 =0.857 dpm/L Pu-239 =0.848 dpm/L
Np-237=0.535 dpm/L Np-237=0.508 dpm/L

28. Bioassay Lab Improvements
Bioassay: fecal method
wet ashing and dissolution in HCL-HF
Diphonix Resin
TEVA+TRU Resin
cartridges not stacked due to possible iron
previously evaporated load plus rinse from TEVA then redissolved, added reductant and loaded onto TRU
Pu, Np (TEVA) and U, Am (TRU)
Sr (Sr Resin)

29. Recent Improvements in Fecal Method
no evaporation of load solution from TEVA to save time
collect load plus minimal rinse from TEVA
add sulfamic acid + ascorbic acid and load to TRU resin
improved Pu stripping with rongalite instead of iodide in strip solution
Also testing:
use of HEDPA strip of Diphonix instead of microwave (minimize HEDPA to minimize phosphate and increase Al in final load solution)
Use sodium peroxide/sodium hydroxide fusion instead of wet ashing

31. Microwave Digestion of Diphonix: Fecal Method

32. Collect load and small rinse ONLY: Eliminated evaporation
Testing using 15 mL strip with 0.04M Rongalite; acidify to 3M HNO3, add Al(NO3)3 and nitrite and load to second TEVA column
Collect load and small rinse
ONLY: Eliminated evaporation 5

33. (2nd Column to Remove all Th-228)
Pu on TEVA Resin-Fecal
(2nd Column to Remove all Th-228)
Adjust acidity of 15 mL strip solution to 3M HNO3 using 4 mLs 16M HNO3
Add 1 mL of 2.5M aluminum nitrate
Add 1mL 3.5 M Sodium Nitrite
Th Removal
3mL 9MHCI/7mL
8MHCI
Rinse
10mL 3MHN03
Pu Elution
20 mL
0.10MHC MHF M rongalite
1mL TEVA Resin

34. Process Lab Improvements
Process samples to support HEU Blenddown processing
Improvements:
Pu and Np are key product specification measurements
Pu-236 tracer for Pu and Np on TEVA resin in HEU and LEU process solutions
1 mL TEVA cartridges to ensure total Th-228 removal (separated twice on TEVA)
use Ti (III) reductant in Pu strip from TEVA

36. Summary Bioassay lab SRS Environmental Monitoring lab work Process lab
Vacuum box technology reduced method time by about 50%
Diphonix-HEDPA may help with difficult soil-fecal samples
Bioassay lab
Improved Pu stripping using rongalite (85% to 99%)
HEDPA to eliminate microwave in fecal analysis
Process lab
Pu-236 tracer use for Pu, Np in process lab on high uranium samples