Determination of trace phenoxy carboxylic acid herbicides in environmental water samples by covalent organic frameworks based solid phase extraction coupled with liquid chromatography-tandem mass spectrometry

The determination of traces levels of pesticide residue in water is crucial for monitoring water quality. In this study, covalent organic frameworks (COFs), namely TAPA-TFPB-COFs were prepared at room temperature (25 °C) and applied as adsorbents for the solid phase extraction (SPE) of phenoxy carboxylic acid herbicides (PCAs). The extraction was followed by analyzation using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Under the optimal conditions, ultrasensitive and specific analysis of PCAs in water samples was achieved. The method exhibited high sensitivity with low limits of detection (0.08-0.28 ng L-1), good linearity in the range of 1.00 to 200 ng L-1 and satisfactory repeatability (intra-day: 3.72-5.30%; inter-day: 2.02-4.04%). The method was successfully applied to the analyzation of trace PCAs in tap, well, and river water and the spiked recoveries were in the range of 81.1-112%. These results indicate that the SPE-LC-MS/MS technique with TAPA-TFPB-COFs as the SPE adsorbent is a promising technique for the detection of trace levels of PCAs in environmental water samples.