Analysis of quinolone antibiotic derivatives in sewage sludge samples by liquid chromatography–tandem mass spectrometry: Comparison of the efficiency of three extraction techniques

This work presents a comparison of three extraction techniques –ultrasound-assisted extraction (USE), microwave-assisted extraction (MAE) and pressurized liquid extraction (PLE) – and evaluates their efficiency in the determination of quinolone antibiotics in sewage sludge samples. Extraction parameters for each technique were optimized using design of experiments, and the compounds were detected and quantified using liquid chromatography–tandem mass spectrometry (LC–MS/MS), operating in positive electrospray ionization (ESI) mode. The use of two selected reaction monitoring transitions for each compound allowed simultaneous quantification and identification in one run. Analytes were separated in less than 10 min. Marbofloxacin and cincophen were used as surrogates for amphoteric and acid quinolones, respectively. The limits of detection (LODs) were between 2 and 5 ng g−1, and the limits of quantification (LOQs) were between 4 and 18 ng g−1 for the various analytes. The inter- and intra-day variability was <7%. Due to the absence of certified reference materials (CRMs), the method was validated using matrix-matched calibration and a recovery assay with spiked samples. Recovery rates were between 97.9% and 104.8%. Statistical comparison demonstrated no significant differences between the three extraction techniques. The methods were successfully applied for the determination of quinolones in sewage sludge samples collected from different wastewater treatments plants (WWTPs) located in the province of Granada (Spain). The analytical methods developed here may be useful for the development of more in-depth studies on the occurrence and fate of these commonly used pharmaceuticals in WWTPs and in the environment.