Dominic Lariviere

RRMC – October 2015

CLOUD POINT EXTRACTION : AN INTERESTING ALTERNATIVE TO LIQUID-LIQUID AND SOLID-PHASE EXTRACTION

Acknowledgments2

Charles LabrecquePhD in September 2015

Researcher at CSST (NIOSH)

Anthony TremblayMSc since 05/2015

Guillaume B.-ChouinardMSc, starting in 01/2016

Why sample preparation is important in radiochemistry?

3

Choices in sample preparation4

Liquid-liquidextraction

Liquid-liquid extraction on a solid support

Solid-liquid extraction

Dietz, M.L. and Horwitz, E.P., LC GC, 1993, 11, 424-436Florek J., Chalifour F., Bilodeau F., Larivière D., Kleitz F., Adv. Funct. Mat., 2014, 24, 2668-2676

Liquid2 µextraction5

P. Zhang, L. Hu, R. Lu, W. Zhou and H. Gao, Anal Methods, 2013, 5376–5385http://www.chromacademy.com/

Dispersive liquid2 µextraction (DLLME) Single drop µextraction (DI-SDME)

DLLME6

B.B. Sadi, C. Li, G.H. Kramer, C.L. Johnson, Q. Ko, E.P.C. Lai, J. Radioanal. Nucl. Chem., 2011, 415-425

Cloud Point Extraction (CPE)7

Cloud Point Extraction (CPE)8

Triton Analogs Tergitol Analogs

Name n CPT (oC) CMC (ppm)X-15 1.5 Insoluble InsolubleX-35 3 Insoluble InsolubleX-45 4.5 Soluble 136X-114 7.5 25 120X-100 9.5 60 159X-102 12 88 267

Name n CPT (oC) CMC (ppm)Np-4 4 Insoluble InsolubleNp-6 6 Insoluble InsolubleNp-7 7 20 39Np-8 8 43 61Np-9 9 54 60Np-10 10 63 55

http://www.dow.com/surfactants/products/

A closer look9

Ligand

Analyte

ComplexLigand-Analyte

Micelle size : 5 nm³

Surface: 14 nm ²

Surface/ volume : ~3

Komaromy-Hiller, G.; Calkins, N. ; von Wandruszka , R. ;Langmuir, 1996, 12, 916-920.

Matrix effects on CPE10

Koshy, L.; Saiyad, A.H.; Rakshit, A.K. Colloid. Polym. Sci., 1992, 274, 582-587;

Nature of the cation Nature of the anion Ionic strenght

Examples of CPE system with actinides11

[12] Laespada, M.E.F.; Pavon, J.L.P.; Cordero, B.M. Analyst 1993, 118, 209-212; [13] Shemirani, F et al. Sep. Sci. Technol. 2005, 40, 2527-2537;[14] Ferreira, H.S.; Bezerra, M.D.; Ferreira, S.L.C. Microchim. Acta 2006, 154, 163-167; [15] Madrakian et al., Talanta 2007, 71, 610-614; [16] Constantinou, E; Pasadilis, I. J. Radioanal. Nucl. Chem. 2010, 286, 461-465; [17] Favre- Réguillon, A et al. J. Chem. Technol. Biotechnol. 2006, 81, 1872-1876; [18] Labrecque, C. et al. Talanta 2013, 107, 284-291; [19] Shariati, S. Yamini, Y.; Zanjani, M.R. J. Hazard. Mater. 2008, 156, 583-590;[20] Constantinou, E.; Pashadilis, I. J. Radioanal. Nucl. Chem. 2011, 287, 261-265.

Analyte Sample Type pH Recovery (%) Instrumentation

U[12-18] Drinking, river and well waters 3,3 to 9,2 55 to quantitative UV-Vis, LSC, ICP-

AES, ICP-MS

U, Th[19] Drinking, river and well waters 6 Quantitative ICP-AES

Th[20] Water 3 60 ± 5 LSC

• How to maintain micellar structures in acidic conditions compatibles with typical sample dissolution.

• Finding the proper ligands and conditions for the selective extraction.

Uranium extraction12

H2DEH[MDP]

Uranium (VI)

ComplexLigand-Analyte

I2

I2

I2

I2

I2

I2

I2H2DEH[MDP]

Iodine is oxydized in iodate as [H+]↑Remplace Iodine with bromine

Labrecque C., Potvin S., Whitty-Léveillé L., Larivière D. (2013) Cloud point extraction of uranium using H2DEH[MDP] in acidic conditions, Talanta, 107:284-291.

Performances with Br213

CPE v 2.014

Sample digestionPu recoveries (%)

Α-spectrometry(n=4) ICP-MS (n=4)

Soil (HQ-G2)

LiBO2:LiBr fusion 95 ± 2 99 ± 9

MW-digestion(HNO3:HF)(10:1) 30 ± 20 N.A.

Urine N.A. 97 93 ± 9

Seawater N.A. 100 95 ± 9SCP-EU-L-3 (Wastewater) N.A. 93 109 ± 4

SCP-EP-L-3 (Drinking water) N.A. 102 100 ± 7

SCP-EP-H-3 (Drinking water) N.A. 98 109 ± 4

IAEA-384 (Sediment) LiBO2:LiBr fusion 102 ± 7 95 ± 9

Labrecque C., Whitty-Léveillé L., Larivière D. (2013), Cloud Point Extraction of Plutonium in Environmental Matrices Coupled to ICP-MS and Alpha Spectrometry in Highly Acidic Conditions, Analytical Chemistry, 85: 10549-10555.

Lanthanides CPE15

i-pr DGA

Ln(III)

ComplexLigand-Analyte

i-prDGA

Br2

Br2

Br2

Br2

Br2

Br2

Br2

Labrecque C., and Larivière D. (2014), Quantification of rare earth elements using cloud point extraction with diglycolamide and ICP-MS for environmental analysis, Analytical Methods, 6:9291-9298.

16Lanthanides Extraction - Results

Extra

ctio

n yi

eld

(%)

Soil (HQ-G2)NIST-2709aBauxite residues

Labrecque C., Lebed, P.J. and Larivière D. (2015), Isotopic signature of selected rare earth elements for nuclear activities profiling using cloud point extraction and ICP-QQQ-MS, Journal of Environmental radioactivity, Submitted for publication.

Simplicity Selectivity PF Green Reusability Aqueous /Acidic media

LLE × ×

IXC × ×

EXC × ~

CPE × N.A.

Extraction approaches – is CPE better?17

LLE: Liquid-liquid extraction IXC : Ionic chromatography

EXC: Extraction chromatography PF: Preconcentration factor

CPE v3.0 – Faster and simpler18

Pu : 99.85 ± 0.05%

Pu : 99.8 ± 0.2%96.5

97.0

97.5

98.0

98.5

99.0

99.5

100.0

100.5

1 5 10 25

Pu e

xtra

ctio

n yi

eld

(%)

Contact time (min)

CPE v3.0 – Automated19

VS

• Extraction occurs on the heated support• Retention phase: Mesoporous Carbon or Glass wool• Elution: Oxalate (MPC) or diluted methanol (GW)

CPE v3.0 – Other Elements20

0 1 2 3 4 50

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[18-crown-6] (M)

Pb

0 2 4 6 80

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[HCl] (M)

Pb

Interestingly, no extraction from Sr…

DCH18C6

21