Quantification of 2,4-dichlorophenoxyacetic acid in environmental samples using imprinted polyethyleneimine with enhanced selectivity as a selective adsorbent in ambient plasma mass spectrometry

Abstract

Detection and quantification of various organic chemicals in the environment is critical to track their fate and control their levels. 2,4-Dichlorophenoxyacetic acid (2,4-D) is a widely applied phenoxy herbicide with potential toxicity to fish and other aquatic organisms. In this study, we address the need for improved detection of 2,4-D by introducing a novel analytical method for its quantification. This method relies on the selective extraction of 2,4-D using MIPs and their subsequent direct analysis using ambient plasma mass spectrometry. During the synthesis, MIPs with various degrees of glycidol (GLY) functionalization were obtained. Experimental data showed that MIPs with no GLY functionalization displayed the highest adsorption capacity. Conversely, MIPs with 30% GLY functionalization exhibited the greatest selectivity for 2,4-D, rendering them valuable for extraction of 2,4-D even in the presence of other contaminants. Finally, the obtained MIPs were applied for quantification of 2,4-D in various water samples through direct analysis using a specially designed ambient plasma mass spectrometry setup. This approach improved the detection limits by 200-fold compared to pure solution analysis. The quantification of 2,4-D in river water samples yielded highly satisfactory recoveries, demonstrating the effective utility of the proposed analytical setup for real-life water sample analysis.

Keywords: Ambient mass spectrometry; Molecularly imprinted polymers; Phenoxy herbicide; Polyethyleneimine; Quantification.