Selective extraction and determination of chlorpyrifos residues from aqueous samples using biochar-functionalized molecularly imprinted polymer combined with high-performance liquid chromatography

Abstract

The concentration of chlorpyrifos (CPF) in aqueous samples was determined using a novel molecularly imprinted dispersive solid-phase extraction (MISPE) approach that was presented in this research. Using a non-covalent molecular imprinting technique, a biochar (BC)-functionalized molecularly imprinted polymers (MIPs) (BC-MIPs) was created. These MIPs were used in dispersive solid-phase extraction (DSPE) in conjunction with high-performance liquid chromatography with photodiode array detection (HPLC-PDA) to detect CPF in aqueous samples with high sensitivity. Using methacrylic acid (MAA) as the monomer and ethylene glycol dimethacrylate (EGDMA) as the cross-linker, BC-MIPs were created using CPF as a template. By using the suggested dispersive solid-phase extraction (DSPE) approach, the efficiency of the synthesized BC-MIPs granules was evaluated. Analytical performance of the devised DSPE-HPLC-PDA technique was assessed under optimal settings. The optimized parameters included extraction time, aqueous sample pH, desorption time and desorption reagents. Compared with the traditional method, the established method has better selective adsorption capacity, reusability and sensitivity for CPF. The suggested method presented that limit of detection and limit of quantification were 1.0 ng/mL and 4.0 ng/mL, along with excellent linear range (4.0-1500 ng/mL) with coefficients of determination (R²=0.9982). The established method was successfully used to determination CPF in aqueous samples from the Baisha River in Qingdao, with the advantages of accuracy (recoveries: 81.2 %-103.6 %, RSDs≤9.2 %), speed (CPF-BC-MIPs-DSPE time: 75 min; HPLC-PDA time: 12 min), selectivity (imprinting factor: 4.24), and economy (50 mg of adsorbent synthesized using cheap straw and 1 mL of solvents), which partially conform to the current advanced principle of "3S+2A" in analytical chemistry. The BC-MIPs granules shown potential for CPF preconcentration in complicated samples and were effective carriers for the selective adsorption of CPF.

Keywords: Biochar-functionalized molecularly imprinted polymers; Chlorpyrifos; Dispersive solid-phase extraction; High-performance liquid chromatography.