Development and validation of an integrated UHPLC-MS/MS and GC-MS method for the simultaneous analysis of three categories of phenolic endocrine disrupting chemicals in surface water

The global concern over emerging contaminants, particularly endocrine-disrupting chemicals (EDCs), has driven the need for advanced detection methods. Phenolic EDCs, such as parabens, bisphenols, and synthetic phenolic antioxidants (SPAs), are widely distributed in the environment and pose risks to reproductive systems and metabolism. With ongoing advancements in research, the development of high-throughput technologies for the simultaneous detection of these phenolic EDCs has become a pressing priority. A sensitive method combining ultra-high performance liquid chromatography-triple quadrupole tandem mass spectrometry (UHPLC-MS/MS) and gas chromatography-mass spectrometry (GC-MS) was developed for the simultaneous determination of three typical classes of phenolic EDCs in aquatic environments, including parabens, bisphenols, and SPAs. Solid-phase extraction (SPE) parameters and instrumental conditions were optimized, achieving recoveries of 64.7%-123% and 64.0%-111% for blank spikes and matrix spikes, respectively, with relative standard deviation below 18%. Detection and quantification limits were determined to be 0.228-0.940 ng L-1 and 0.758-3.13 ng L-1, respectively. The method was successfully applied to 23 surface water samples, and 10 EDCs were detected. Notably, bisphenols and SPAs in the Qiantang River displayed a clear increasing trend toward the downstream. SPAs exhibited the highest concentrations, with oxidation by the pi-system being the predominant pathway responsible for the transformation to degradants like BHT-Q and BHT-quinol. This method offers reliable detection and quantification of multiple phenolic EDCs in water, providing a valuable tool for environmental monitoring, risk assessment, and regulatory management of EDCs contamination.