Selective solid phase extraction of lanthanides from tap and river waters with ion imprinted polymers.
For the first time, an ion imprinted polymer (IIP) able to selectively extract simultaneously all the lanthanide ions was successfully synthesized in acetonitrile using Nd3+as a template ion, methacrylic acid as a complexing monomer, and ethylene glycol dimethacrylate as a cross-linker. A non-imprinted polymer (NIP) was synthesized under the same conditions as those of the IIP, but in the absence of the template ion. After the removal of the template ions, grounding and sieving, the IIP particles were packed in solid phase extraction (SPE) cartridges. The selectivity of the IIP was evaluated by comparing its behavior with the one of the NIP. Each SPE step (percolation, washing, and elution) was optimized in order to find the best compromise between the selectivity and the extraction recoveries. Using the optimized SPE conditions, the extraction recoveries of eight lanthanide ions representative of the lanthanide family were higher than 77% with an average value of 83% with the IIP, whereas, in the case of the NIP, they ranged between 14 and 36% and they were below 3% for the interfering ions from alkali, transition, and post-transition metal families with the IIP. A first evaluation of the reproducibility of the SPE profiles was carried out by performing statistical tests on the data obtained with several cartridges filled with particles obtained from two different IIP and NIP syntheses. Promising results were obtained. The specific capacity, i. e. the adsorption capacity of Nd3+ions by the specific cavities of the imprinted polymer, was about 9 mg of Nd3+per gram of IIP (60 μmol g-1), which is more than enough for the extraction of the lanthanide ions at trace levels. The breakthrough volume was about 1 mL per mg of IIP, leading to an enrichment factor of 15, which allows not only to selectively extract the lanthanides but also to concentrate them. Finally, the imprinted polymer was successfully used to selectively extract lanthanides from tap and river waters spiked at 1 μg L-1.
Laboratory of Analytical, Bioanalytical Sciences and Miniaturization (LSABM), UMR CBI 8231, ESPCI Paris, PSL Research University, Paris, France; UPMC, Sorbonne Universités, Paris, France.
Manel
M
Moussa
Laboratory of Analytical, Bioanalytical Sciences and Miniaturization (LSABM), UMR CBI 8231, ESPCI Paris, PSL Research University, Paris, France.
Massamba Mbacké
MM
Ndiaye
Laboratory of Analytical, Bioanalytical Sciences and Miniaturization (LSABM), UMR CBI 8231, ESPCI Paris, PSL Research University, Paris, France.
Thomas
T
Pinta
Laboratory of Analytical, Bioanalytical Sciences and Miniaturization (LSABM), UMR CBI 8231, ESPCI Paris, PSL Research University, Paris, France; UPMC, Sorbonne Universités, Paris, France.
Valérie
V
Pichon
CEA Saclay, DEN, DANS, DPC, SEARS, LANIE, Gif-sur-Yvette, France.
Thomas
T
Vercouter
Laboratory of Analytical, Bioanalytical Sciences and Miniaturization (LSABM), UMR CBI 8231, ESPCI Paris, PSL Research University, Paris, France; CNRS, UMR CBI 8231, Paris, France. Electronic address: nathalie.delaunay@espci.fr.
Nathalie
N
Delaunay
D000097:Acetonitriles / Q000737:chemistry; D028581:Lanthanoid Series Elements / Q000032:analysis / Q000302:isolation & purification*; D054802:Molecular Imprinting; D011109:Polymethacrylic Acids / Q000138:chemical synthesis* / Q000737:chemistry; D045483:Rivers / Q000737:chemistry*; D052616:Solid Phase Extraction / Q000379:methods*; D014867:Water / Q000737:chemistry*
D000097:Acetonitriles; D028581:Lanthanoid Series Elements; D011109:Polymethacrylic Acids; D014867:Water; C030613:polymethacrylic acid; C032159:acetonitrile
Ion imprinted polymer; Lanthanides; River water; Solid-phase extraction (SPE); Tap water