Comparison and Optimization of Pretreatment Methods for Emerging Contaminants and Application in Industrial Wastewater Samples
The pretreatment of trace emerging contaminants in environmental matrices is challenging due to diverse methods and uncertain applicability. This study compared solid-phase extraction (SPE) and liquid-liquid extraction (LLE) for extracting endocrine-disrupting compounds (EDCs), particularly phthalate esters (PAEs), using laboratory-spiked blank samples. LLE achieved satisfactory recoveries for PAEs at spike levels below 4 μg·L−1, enabling detection of five PAEs including diisodecyl phthalate (DIDP), with improved efficiency via repeated extraction. SPE offered lower detection and quantification limits, higher accuracy and sensitivity, and achieved high recoveries for 12 EDCs and 10 antibiotics at spike levels ≥0.2 μg·L−1, with detection limits as low as 0.1–6.4 ng·L−1. The developed SPE coupled with liquid chromatography-Orbitrap mass spectrometry (LC-Orbitrap MS) method was applied to industrial wastewater samples. Across five industrial sectors (coatings, rubber, pharmaceuticals, inks, and materials technology), five antibiotics and ten EDCs were detected, with total concentrations ranging from 0.03–0.56 μg·L−1 and 0.07–1.91 μg·L−1, respectively. Sector-specific profiles emerged: rubber industry effluent was dominated by dibutyl phthalate (DBP) at 1.07 μg·L−1, while pharmaceutical effluent featured sulfamonomethoxine (SMM) at 0.34 μg·L−1. This systematic evaluation demonstrates that SPE-LC-Orbitrap MS is robust for complex matrices, providing a technical foundation for accurate quantification of emerging contaminants in industrial wastewater.