Microcystins (MCs; cyclic heptapeptides) are produced by freshwater cyanobacteria and cause public health concern in potable water supplies. There are more than 60 types of MCs identified to date, of which MC-LR is the most common found worldwide. For MC-LR, the WHO has established a threshold value of 1 μg L−1 for drinking water. The present MCs removal methods such as coagulation, flocculation, adsorption, and filtration showed low efficiency for removing dissolved MC fraction from surface waters to the stipulated limit prescribed by WHO based on MC health impacts. The search for cost-effective and efficient removal method is still warranted for remediation of dissolved MC-LR-contaminated water resources.
Materials and methods
Molecularly imprinted polymer (MIP) adsorbent has been prepared using non-covalent imprinting approach. Using MC-LR as a template, itaconic acid as a functional monomer, and ethylene glycol dimethacrylate as a cross-linking monomer, a MIP has been synthesized. Computer simulations were used to design effective binding sites for MC-LR binding in aqueous solutions. Batch binding adsorption assay was followed to determine binding capacity of MIP under the influence of environmental parameters such as total dissolved solids and pH.
Results and discussion
The adsorptive removal of MC-LR from lake water has been investigated using MIPs. The MIP showed excellent adsorption potential toward MC-LR in aqueous solutions with a binding capacity of 3.64 μg mg−1 which is about 60% and 70% more than the commercially used powdered activated carbon (PAC) and resin XAD, respectively. Environmental parameters such as total organic carbon (represented as chemical oxygen demand (COD)) and total dissolved solids (TDS) showed no significant interference up to 300 mg L−1 for MC-LR removal from lake water samples. It was found that the binding sites on PAC and XAD have more affinity toward COD and TDS than the MC-LR. Further, the adsorption capacity of the MIP was evaluated rigorously by its repeated contact with fresh lake water, and it was found that the adsorption capacity of the MIP did not change even after seven adsorption/desorption cycles. The contaminated water of MC-LR (1.0 μg L−1) of 3,640 L could be treated by 1 g of MIP with an estimated cost of US $1.5.
The adsorption capacity of the MIP is 40% more than commercially used PAC and resins and also the polymer showed reusable potential which is one of the important criteria in selection of cyanotoxins remediation methods.
This is a preview of subscription content, log in to check access.
Buy single article
Instant access to the full article PDF.
Price includes VAT for USA
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
This is the net price. Taxes to be calculated in checkout.
American Water Works Association (AWWA)/American Public Health Association (APHA) (2001) Standard methods for examination of water and wastewater. AWWA/APHA, New York
Antoniou MG, de la Cruz AA, Dionysiou DD (2005) Cyanotoxins: new generation of water contaminants. J Environ Engg 131:1239–1243
Antoniou MG, de la Cruz AA, Dionysiou DD (2010) Intermediates and reaction pathways from the degradation of microcystin-LR with sulfate radicals. Environ Sci Technol 44:7238–7244
Azevedo SMFO, Carmichael WW, Jochimsen EM, Rinchart KL, Lau S, Shaw SR, Eaglesham GK (2002) Human intoxication by microcystins during renal dialysis treatment in Caruaru-Brazil. Toxicol 181:441–446
Campinas M, Rosa MH (2006) The ionic strength effect on microcystin and natural organic matter surrogate adsorption onto PAC. J Colloid Interf Sci 299:520–529
Chianella I, Lotierzo M, Piletsky SA, Tothill IE, Chen B, Karim K, Turner APF (2002) Rational design of the polymer specific for microcystin-LR using a computational approach. Anal Chem 74:1288–1293
Chianella I, Piletsky SA, Tothill IE, Chen B, Karim K, Turner APF (2003) MIP-based solid phase extraction cartridges combined with MIP-based sensors for the detection of microcystin-LR. Biosens Bioelectron 18:119–127
Choi H, Antoniou MG, Pelaez M, de la Cruz AA, Shoemaker JA, Dionysiou DD (2007) Mesoporous nitrogen-doped TiO2 for the photocatalytic destruction of the cyanobacterial toxin microcystin-LR under visible light irradiation. Environ Sci Technol 41:7530–7535
Donati C, Drikas M, Hayes R, Newcombe G (1994) Microcystin-LR adsorption by powdered activated carbon. Water Res 28:1735–1742
Falconer IR (1999) An overview of problems caused by toxic blue-green algae (cyanobacteria) in drinking and recreational water. Toxicol 14:5–12
Karim K, Breton F, Rouillon R, Piletska EV, Guerreiro A, Chianella I, Piletsky SA (2005) Monomers for effective molecularly imprinted polymers. Adv Drug Deliv Rev 57:1795–1808
Krupadam RJ, Bhagat B, Wate SR, Bodhe GL, Sellergren B, Anjaneyulu Y (2009) Fluorescence spectrophotometer analysis of polycyclic aromatic hydrocarbon in environmental sample based on solid phase extraction using molecularly imprinted polymer. Environ Sci Technol 43:2871–2877
Lambert TM, Holmes CFB, Hrudey SE (1994) Microcystin class of toxins: health effects and safety of drinking water supplies. Environ Rev 2:167–186
Lawton LA, Robertson PK (1999) Physico-chemical treatment methods for the removal of microcystins (cyanobacterial hepatotoxins) from potable waters. Chem Soc Rev 28:217–224
Lee J, Walker HW (2006) Effect of process variables and natural organic matter on removal of microcystin-LR by PAC-UF. Environ Sci Technol 40:7336–7342
Mayes AG, Whitcombe MJ (2005) Synthetic strategies for the generation of molecularly imprinted organic polymers. Adv Drug Deliv Rev 57:1742–1778
Nicholson BC, Rositano J, Burch MD (1994) Destruction of cyanobacterial peptide hepatotoxins by chlorine and chloramine. Water Res 28:1297–1305
Pelaez M, Falaras P, Likodimos V, Kontos AG, de la Cruz AA, O’shea K, Dionysiou DD (2010) Synthesis, structural characterization and evaluation of sol–gel-based NF-TiO2 films with visible light-photoactivation for the removal of microcystin-LR. Appl Catalysis B 99:378–387
Pendleton P, Schumann R, Wong SH (2001) Microcystin-LR adsorption by activated carbon. J Colloid Interf Sci 240:1–8
Sabourin L, Ansell RJ, Mosbach K, Nicholls IA (1998) Molecularly imprinted polymer combinatorial libraries for multiple simultaneous chiral separations. Anal Commun 35:285–287
Sibrian-Vazquez M, Spivak DA (2003) Enhanced enantioselectivity of imprinted polymers formulated with novel crosslinking monomers. Macromolecules 36:5105–5113
Stoner RD, Adams WH, Slatkin DN, Siegelman HW (1989) The effect of single L-amino acid substitutions on the lethal potencies of the microcystins. Toxicon 27:825–828
Vlatakis G, Andersson LL, Muller R, Mosbach K (1993) Drug assay using antibody mimics made by molecular imprinting. Nature 361:645–657
World Health Organization (WHO) (1998) Cyanobacterial toxins: microcystin-LR. Guidelines for drinking water quality. WHO, Geneva, pp 95–110
Wulff G (2002) Enzyme-like catalysis by molecularly imprinted polymers. Chem Rev 102:1–27
Wulff W, Sarhan A (1972) Use of polymers with enzyme-analogous structures for the resolution of racemates. Angew Chem Ind Ed Engl 11:341–344
Yang H, Gong A, He H, Zhou L, Wei Y, Lv L (2006) Adsorption of microcystins by carbon nanotubes. Chemosphere 62:142–148
Zimmerman SC, Lemcoff NG (2004) synthetic hosts via molecular imprinting: are universal synthetic antibodies realistically possible? Chem Commun 1:5–14
R.J.K gratefully acknowledges the Council of Scientific and Industrial Research, New Delhi and Planning Commission of India, Government of India for financial support under Supra Institutional Project: Environmental Molecular Science (grant no. SIP-16/3.3)
Responsible editor: Philippe Garrigues
Electronic supplementary material
Below is the link to the electronic supplementary material.
(DOC 1176 kb)
About this article
Cite this article
Krupadam, R.J., Patel, G.P. & Balasubramanian, R. Removal of cyanotoxins from surface water resources using reusable molecularly imprinted polymer adsorbents. Environ Sci Pollut Res 19, 1841–1851 (2012). https://doi.org/10.1007/s11356-011-0703-1
- Water remediation molecular imprinting
- Selective adsorption