Development of Molecular Imprinted Polymers (MIPs) for the Selective Removal of Carbamazepine from Aqueous Solution

The occurrence and removal of trace organic contaminants in the aquatic environment has become a focus of environmental concern. For the selective removal of carbamazepine from loaded waters molecularly imprinted polymers (MIPs) were synthesized with carbamazepine as template. Parameters varied were the type of monomer, crosslinker, and porogen, the ratio of starting materials, and the synthesis temperature. Best results were obtained with a template to crosslinker ratio of 1:20, toluene as porogen, and methacrylic acid (MAA) as monomer. MIPs were then capable to recover carbamazepine by 93% from a 10-5 M landfill leachate solution containing also caffeine and salicylic acid. By comparison, carbamazepine recoveries of 75% were achieved using a nonimprinted polymer (NIP) synthesized under the same conditions, but without template. In landfill leachate containing solutions carbamazepine was adsorbed by 93-96% compared with an uptake of 73% by activated carbon. The best solvent for desorption was acetonitrile, with which the amount of solvent necessary and dilution with water was tested. Selected MIPs were tested for their reusability and showed good results for at least five cycles. Adsorption isotherms were prepared with carbamazepine solutions in the concentration range of 0.01 M to 5*10-6 M. The heterogeneity index showed a more homogenous binding site distribution.




References:
[1] T. A. Ternes, "Occurrence of drugs in German sewage treatment plants
and rivers," Water Res., vol. 32, pp. 3245-3260, Nov. 1998.
[2] T. A. Ternes, M. Bonerz, T. J. Schmidt, 2001. "Determination of neutral
pharmaceuticals in wastewater and rivers by liquid chromatography-
electrospray tandem mass spectrometry," J. Chromatogr. A, vol. 938, pp.
175-185, Dec. 2001.
[3] T. A. Ternes, J. St├╝ber, N. Herrmann, D. McDowell, A. Ried, M.
Kampmann, B. Teiser, "Ozonation: A tool for removal of
pharmaceutical contrast media and musk fragrances from wastewater?,"
Water Res., vol. 37, pp. 1976-1982, Apr. 2003.
[4] H. Zhang, H. Yamada, S.-E. Kim, H.-S. Kim, H. Tsuno, "Removal of
endocrine disrupting chemicals by ozonation in sewage treatment,"
Water Sci. Technol., Vol. 54, pp. 123-132, 2006.
[5] C. Zwiener, F. H. Frimmel, "Oxidative treatment of pharmaceuticals in
water," Water Res., vol. 34, pp. 1881-1885, Apr. 2000.
[6] R. Andreozzi,V. Caprio, R. Marotta, A. Radovnikovic, "Ozonation and
H2O2/UV treatment of clofibric acid in water: A kinetic investigation," J.
Hazard. Mater., vol. 103, pp. 233-246, Oct. 2003.
[7] D. Vogna, R. Marotta, R. Andreozzi, A. Napolitano, M. d-Ischia,
"Kinetic and chemical assessment of the UV/H2O2 treatment of
antiepileptic drug carbamazepine" Chemosphere, vol. 54, pp. 497-505,
Jan. 2004.
[8] T. E. Doll, F. H. Frimmel, "Photocatalytic degradation of
carbamazepine, clofibric acid and iomeprol with P25 and Hombikat
UV100 in the presence of natural organic matter (NOM) and other
organic water constituents," Water Res., vol. 39, pp. 403-411, Jan.-Feb.
2005.
[9] S. Esplugas, D. M. Bila, L. G. T. Krause, M. Dezotti, "Ozonation and
advanced oxidation technologies to remove endocrine disrupting
chemicals (EDCs) and pharmaceuticals and personal care products
(PPCPs) in water effluents," J. Hazard. Mater., vol. 149, pp. 631-642,
Nov. 2007.
[10] B. R. Locke, M. Sato, P. Sunka, M. R. Hoffmann, J.-S. Chang,
"Electrohydraulic discharge and nonthermal plasma for water
treatment," Ind. Eng. Chem. Res., vol. 45, pp. 882-905, Feb. 2006.
[11] H. Krause, B. Schweiger, J. Schuhmacher, S. Scholl, U. Steinfeld,
"Degradation of the endocrine disrupting chemicals (EDCs)
carbamazepine, clofibric acid, and iopromide by corona discharge over
water," Chemosphere, vol. 75, pp. 163-168, Apr. 2009.
[12] Y. Zhang, J. Zheng, X. Qu, H. Chen, "Design of a novel non-equilibrium
plasma-based water treatment reactor," Chemosphere, vol. 70, pp. 1518-
1524, Feb. 2008.
[13] T. A. Ternes, M. Meisenheimer, D. McDowell, F. Sacher, H.-J. Brauch,
B. Haist-Gulde, G. Preuss, U. Wilme, N. Zulei-Seibert, "Removal of
Pharmaceuticals during Drinking Water Treatment," Environ. Sci. and
Technol., vol. 36, pp. 3855-3863, Sept. 2002.
[14] M. Le Noir, A.-S. Lepeuple, B. Guieysse, B. Mattiasson, "Selective
removal of 17¶Çêò-estradiol at trace concentration using a molecularly
imprinted polymer," Water Res., vol. 41, pp. 2825-2831, June 2007.
[15] A. J. Hall, M. Emgenbroich, B. Sellergren, "Imprinted polymers," in
Top. Curr. Chem., vol. 249, pp. 317-349, Springer-Verlag Berlin
Heidelberg, 2005.
[16] W. Sch├╝ssler, M. Sengl, "Arzneimittel in der Umwelt (Pharmaceuticals
in the environment)," Materialien Nr. 114, Bayerisches Landesamt f├╝r
Wasserwirtschaft, Germany, Aug. 2004.
[17] T. Heberer, "Occurrence, fate, and removal of pharmaceutical residues
in the aquatic environment: a review of recent research data," Toxicol.
Lett., vol. 131, pp. 5-17, May 2002.
[18] J. W. Metzger, ÔÇ×Drugs in municipal landfills and landfill leachate," In:
K├╝mmerer, K. (Ed.). Pharmaceuticals in the Environment: Sources,
Fate, Effects and Risks, Springer, Berlin, 2004, pp. 133-137.
[19] B. Ferrari, N. Paxéus, R. Lo Giudice, A. Pollio, J. Garrica,
"Ecotoxicological impact of pharmaceuticals found in treated
wastewaters: study of carbamazepine, clofibric acid, and diclofenac,"
Ecotoxicol. Environ. Saf., vol. 55, pp. 359-370, July 2003.
[20] P. M. Álvarez, F. J. Beltrán, V. Gómez-Serrano, J. Jaramillo, E. M.
Rodríguez, "Comparison between thermal and ozone regenerations of
spent activated carbon exhausted with phenol," Water Res., vol. 38, pp.
2155-2165, Apr. 2004.