Chlorophenol’s ultra-trace analysis in environmental samples by chitosan–zinc oxide nanorod composite as a novel coating for solid phase micro-extraction combined with high performance liquid chromatography

Abstract

In this study, a simple, novel, and efficient preconcentration method has been developed for the determination of some chlorophenols (4-chlorophenol, 2,5-dichlorophenol, 2,3-dichlorophenol, and 2,4,6-trichlorophenol) using a direct solid phase microextraction (D-SPME) based on chitosan–ZnO nanorod composite combined with high performance liquid chromatography (HPLC). A one step-novel hydrothermal method was demonstrated on the fabrication of ZnO nanorods arrayed on the fused silica fiber in the chitosan hydrogel solution (CZNC) as a new coating of SPME fiber. The coating was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) instruments. The CZNC coating has combined the merits of both ZnO nanorods and chitosan hydrogel; it has several improvements such as increased extraction efficiency of chlorophenols and longer life time (over 80 cycles of D-SPME-HPLC operation). Experimental design method was used for optimization of extraction conditions and determination of four chlorophenols in water samples by SPME-HPLC-UV method. The calibration curves were linear from 5 to 1000µgL−1 for analytes, and the limits of detection were between 0.1 and 2µgL−1. Single fiber repeatability and fiber-to-fiber reproducibility were in the range of 5.8–10.2% and 8.8–14.5%, respectively. The spiked recoveries at 50µgL−1 for environmental water sample were in the range of 93–102%.