Abstract
In the present study, a liquid chromatography-mass spectrometry (LC-MS) method has been developed and validated to monitor traces of microcystins (MCs) in lake and marine waters. The molecularly imprinted polymer (MIP) formulated with itaconic acid as the functional monomer and ethylene glycol dimethacrylate as the crosslinking monomer has been used to selectively enrich MCs from the aqueous solutions. The extraction capacity and selectivity of MIP was higher when comparison with conventionally used resin XAD and powdered activated carbon (PAC). The MIP showed an outstanding selectivity for microcystin-LR (MC-LR) in a mixture of MCs from aqueous solutions in the pH range 6-9. The LC-MS analysis of MCs after MIP extraction showed an excellent linearity in the working range (R2=0.998) with high repeatability (RSD%, <6.3) and recoveries above 90%. Interference of dissolved ions and solution pH on MCs trace quantification in the lake and marine water samples were quantified. The limits of quantification (LOQ) and lower limit of detection (LOD) for the MC-LR were 10 and 1 ng L-1, respectively, which satisfies the strictest World Health Organization standard for MC-LR in drinking water (1 ng mL-1). The proposed analytical approach is simple, efficient and comparable with the detection limit of the traditional and expensive ELISA method of MCs analysis.
Highlights
The production and release of cyanotoxins by cyanobacteria in freshwaters around the world has been well documented [1,2]
The binding capacity of molecularly imprinted polymer (MIP) with the formulation of methacrylic acid (MAA) - ethylene glycol dimethacrylate (EGDMA) and AFMSA -EGDMA were less pronounced than the MIP prepared with itaconic acid (IA)-EGDMA formulation; this could be explained based on formation of the lower affinity binding sites during molecular imprinting of former cases
The extraction capacities of the MIP prepared with IA-EGDMA formulation showed superior MCs binding capacity than those of most MIPs reported in the literature [25,26]
Summary
The production and release of cyanotoxins by cyanobacteria in freshwaters around the world has been well documented [1,2]. Three MIPs specific for MC-LR were prepared with different formulations and optimized the SPE conditions for MC-LR analysis in lake and marine waters by LC/MS detection. The selectivity of the MIP was determined by comparing the binding capacity of MCLR on to the NIP and MIP packed SPE cartridges by analyzing 1 mL of samples of lake and marine waters with the optimized operational conditions.
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