Matrix and High Loading Effects on Eichrom Resins. Dan McAlister and Phil Horwitz Eichrom Workshop October 31, 2012

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1 Matrix and High Loading Effects on Eichrom Resins Dan McAlister and Phil Horwitz Eichrom Workshop October 31, 2012

2 Examples of High Salt Matrices Sea Water (35 g/l, NaCl, KCl, MgCl 2 and CaCl 2 ) Urine (30 70 g/l, Na + (3 4g), K + (1 2g), Ca 2+ ( g), PO 4 3 (1 2g), SO 4 2 (1 4g), Mg (40 200mg), NH 4+ (0.3 1g), I (50 250mg), Cl (9 16g)) Soil (Na, K, Ca, Mg, Al, Fe, SiO 4 4, SO 4 2, PO 4 3, CO 3 2 ) Precipitations (FeOH 3, CaHPO 4, BaSO 4, MnO 2 ) Uranium Materials

3 Basic Principle of Metal Ion Extraction Extractant Solvent Organic Phase or Resin Metal Ion Water Counter Ion Aqueous Phase The magnitude of the extraction depends on: a. Hydration Energies of the Cations and Anions b. Bond Energy Between the Cation and Extractant c. Solvation Energy of the Extractant and the Complex d. Activities of ions participating in the extraction

4 Ways Matrices Can Affect Separations 1) Co extraction with desired analyte 2) Complexation of the analyte or 3) Decrease or Increase Solubility or 4) Complexation of competing species 5) Changing the activity of ions or 6) Masking Impurities in Extractant

5 Common Matrix Components H + Li + Na + NH 4 + K + K + on Sr Resin Solubility Mass following evaporation (NH 4+ ) Activity of counter ion/magnitude of extraction (Li + )

6 Mean Activity :1 LiNO 3 HNO 3 2:1 Al(NO 3 ) 3 1:1 NaNO (NH 4 )NO 3 3 KNO Molarity

7 Common Matrix Components Mg 2+ Ca 2+ Sr 2+ Ba 2+ Ca 2+, Ba 2+, Sr 2+ on Sr Resin Ca 2+ on DGA Solubility Activity of counter ion/magnitude of extraction

8 Common Matrix Components Fe 2+ /Fe 3+ Al 3+ Fe 3+ on TRU Red/Ox states (Fe/Np) Bind complexing anions (SO 2 4 /PO 3 4 ) Activity of counter ion/magnitude of extraction (Al)

9 Common Matrix Components ClO 4 NO 3 Cl F Oxalate 2 SO 4 2 PO 4 3 Solubility Extractability of analytes Stoichiometry Charge of complex Hydration Energies

10 Common Matrix Components 10 4 k' -Ra on Sr Resin Calculated Hydration Energies of Selected Anions HClO 4 HI HBr HNO [Acid], M Anion ClO 4 I SCN Br NO 3 Cl F SO 4 2 CO 3 2 PO 4 3 Hydration Energy (kj/mol)

11 Tolerates High Levels of nearly all matrix cations High Fe(III) can impact separations in HCl Complexing anions can reduce uptake of actinides.

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13 10 5 k' Fe on UTEVA vs HCl um, 22(1) o C, 1 hr equilibration 10 4 Fe(III) Fe(III) can be extracted from HCl media. k' Addition of ascorbic acid reduces Fe(III) to Fe(II). Fe(II)/ascorbic acid can reduce other analytes Pu(IV) to Pu(III) Np(V)/(VI) to Np(IV) M ascorbic acid [HCl],

14 Tolerates High Levels of nearly all matrix cations High Fe(III) can impact separations particularly in HCl Complexing anions can reduce uptake of actinides.

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16 Tolerates High Levels of: Alkalai metals Alkaline earths Aluminum Am/Cm(III) uptake can be reduced by high: Fe(III) Lanthanides(III) Sulfate Oxalate

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18 k' on TRU Resin vs Ca k' on TRU Resin vs Fe(III) 3M HNO 3 3M HNO 3 k' 10 2 Pr Nd Sm Ce Eu Gd La k' 10 2 Pr Nd Ce Sm Eu La Gd k' Tb-Lu > [Ca], mg/l k' Tb-Lu > [Fe(III)], mg/l

19 Tolerates High Levels of: Na, Fe, Al, Mg Sr uptake can be reduced by high: K Ca Sr (>5mg)

20 Effect of Matrix Constituents on Strontium Retention Sr Resin 3 MHNO k' Sr on Sr Resin vs Ca and Mg m, 2 h, 21(1) o C Mg 10 2 k'-sr Ca M NO 3 - (total from HNO 3 and M(NO 3 ) [M 2+ ], M

21 Ionic Sr 2+ (1.18) Pb 2+ (1.19) Ca 2+ (1.00) Mg 2+ (0.72) Radii(Å) Na + (1.02) K + (1.38) k' Sr NHon Sr Resin vs Ca and Mg 4+ (1.44) H 3 O + (1.43) m, 2 h, 21(1) o C 10 3 Mg 10 2 k'-sr Ca M NO 3 - (total from HNO 3 and M(NO 3 ) [M 2+ ], M

22 k' Sr(II) on DGA, Normal M HNO k' Sr Na + K + DGA Resin is an alternative for Sr Separation from high potassium samples [K + ] or [Na + ], M

23 k on DGA Resin, Normal Am(III) Pu(IV) Th(IV) 10 3 Ca k' U(VI) Tc(VII) k' Sr Pb [HNO 3 ], M [HNO 3 ], M

24 10 4 k' on DGA Resin vs Mg m, 2 h, 21(1) o C La Ce Tolerates High Levels of: Na, K Mg Fe(II)/Fe(III) Al k' 10 1 k' Y, Pr-Lu > 10 4 Uptake of Ac, U(VI) and light lanthanides can be reduced by high: Ca M NO 3 - (total from HNO 3 and M(NO 3 ) 2 High Fe(III) concentrations in HCl and improve uptakes [Mg], M

25 10 4 k' on DGA Resin vs Ca m, 2 h, 21(1) o C k' La Pr Ce Nd Sm k' Y, Tb-Lu > 10 4 High Ca concentrations in nitrate media significantly reduce the uptake of Ac, La Sm, U(VI). Am/Cm uptake still remain >10 3 for Ca concentrations up to 3M M NO 3 - (total from HNO 3 and M(NO 3 ) [Ca], M

26 Gd Eu k' on DGA Resin vs Fe m, 2 h, 21(1) o C 3M HCl High Fe(III) concentrations in chloride media significantly can increase the uptake of metal ions on DGA. k' 10 2 Sm Nd Pr 10 1 Ce La 10 0 k' Tb-Lu > [Fe], ppm

27 Elution on TODGA Resin, 2mL Cartridge, m, 2mL/min, 21(1) o C 10 4 Fe Rinse Strip Rinse Strip 10 3 Load 4M HCl mg Fe 9M 2M 0.1M 1M HCl HCl Bioxalate HNO ppm Pb Ba Mg Sr Ca La Y Th U 10-1 Bi 10-2 >90% La Bed Volumes