Rapid Broad‐Polarity Screening of 459 Emerging Contaminants in Environmental Waters by Online Polarity‐Partitioned Two‐Dimensional Liquid Chromatography‐Tandem Mass Spectrometry

A rapid, broad-polarity targeted screening method based on online polarity-partitioned two-dimensional liquid chromatography-tandem mass spectrometry (2D-LC-MS/MS) was developed for the determination of 459 emerging contaminants (ECs) in environmental waters. The target panel covered nine classes, including herbicides, fungicides, insecticides, pharmaceuticals and personal care products, hormones, plant growth regulators, per- and polyfluoroalkyl substances, flame retardants, and preservatives. In this configuration, highly polar compounds were retained and separated in the hydrophilic interaction chromatography (HILIC) dimension, whereas weakly retained medium- and low-polarity compounds were transferred online, diluted, and further separated in the reversed-phase liquid chromatography (RPLC) dimension. This polarity-partitioned HILIC/RPLC workflow expanded the chemical coverage of targeted EC monitoring and enabled the analysis of target compounds within 28 min. Combined with a lyophilization-based sample preparation procedure, the method was validated in terms of linearity, accuracy, precision, recovery, and matrix effects. The validated method was then applied to tap water and wastewater samples to demonstrate its applicability for broad-spectrum environmental monitoring. Five ECs, mainly including neonicotinoid insecticides and triethyl phosphate, were detected in tap water at concentrations of 0.26-7.65 µg/L, while nine ECs, mainly including sulfonamide antibiotics, pesticides, triethyl phosphate, carbamazepine, and perfluorooctanoic acid, were found in wastewater at 0.37-5.37 µg/L. These results demonstrate that the developed online 2D-LC-MS/MS method provides a rapid and efficient tool for screening ECs with diverse physicochemical properties in environmental waters and supporting high-throughput water quality surveillance.