• • LLE achieved satisfactory recoveries for PAEs only at spike levels <4 μg·L−1, limiting its use to low-concentration scenarios; repeated extraction improved efficiency, but SPE outperformed LLE in sensitivity and accuracy.
• • SPE enabled detection of 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, making it suitable for trace analysis in complex matrices.
• • In industrial wastewater, total concentrations of antibiotics and EDCs ranged from 0.03–0.56 μg·L−1 and 0.07–1.91 μg·L−1, respectively, with rubber effluent dominated by DBP (1.07 μg·L−1) and pharmaceutical effluent by SMM (0.34 μg·L−1), indicating sector-specific contamination profiles.
• • The SPE-LC-Orbitrap MS method proved adaptable to complex industrial matrices, achieving reliable quantification of emerging contaminants, which is critical for regulatory monitoring and risk assessment.