Highly sensitive detection of organophosphorus pesticides in water using a carboxyl-functionalized magnetic covalent organic framework

Abstract

The development of novel methods for the precise quantification of organophosphate pesticides (OPPs), with enhanced accuracy, sensitivity, and efficiency, is crucial for environmental monitoring and human health risk assessment. In this study, Fe3O4@SiO2@COF-COOH magnetic core–shell nanoparticles were synthesized by coating a carboxyl-functionalized covalent organic framework (COF-COOH) onto the surface of amino-modified silica-coated iron(III) oxide particles (Fe3O4@SiO2-NH2). The incorporation of carboxyl groups, covalent organic framework and magnetic properties imparted superior performance to the adsorbent in magnetic solid-phase extraction (MSPE) of polar compounds from complex sample matrices. An analytical method based on Fe3O4@SiO2@COF-COOH coupled with GC–MS/MS was developed for the determination of eight organophosphate pesticide residues in river water near farmland. The established method displays good linearity in the range of 0.1–500 ng/mL for four OPPs and 1–2000 ng/mL for the other four, with correlation coefficients between 0.9903–0.9983. The LODs (S/N = 3) and LOQs (S/N = 10) were determined to be in the ranges of 0.53–9.6 ng/L and 1.8–31.9 ng/L, respectively. The adsorption mechanism was characterized by density functional theory calculations. Furthermore, the established method was successfully applied to analyze the distribution of trace OPPs in real river water samples collected from various cities in Henan Province. Its rapid, straightforward, and efficient ability to enrich trace levels of OPPs from complex real-world samples makes it a valuable tool for environmental monitoring, food safety, and human health management.