Simultaneous analysis of multiclass antibiotic residues in complex environmental matrices by liquid chromatography with tandem quadrupole mass spectrometry

Abstract

A simultaneous extraction and cleanup method was optimized and validated for the determination of 40 antibiotics from cephalosporin, fluoroquinolone, lincosamide, macrolide, nitroimidazole, quinolone, sulfonamide and tetracycline groups in sediments by liquid chromatography with tandem quadrupole mass spectrometry (LC-MS/MS). The method involved hydration of freeze-dried sediment sample (2.0 g) with 2.5 ml of 0.1 M Na-EDTA McIlvaine buffer and extraction with 5 ml of MeOH and MeCN (1:3 v/v) followed by dispersive solid phase extraction by using 100 mg mix of C18 and PSA (1:2 w/w) and 50 mg MgSO₄ prior to LC-MS/MS analysis. The method was validated for 10, 20, 50 and 100 µg/kg spiking levels by using blank sediment sample obtained from a drinking water reservoir according to the guidelines of European Commission Decision (2002) 2002/657/EC. The method produced clean extracts with generally low matrix effect during LC-MS/MS analysis. The mean recoveries ranged between 24-162%, 48-151%, 51-159%, and 50-149% for 10, 20, 50 and 100 µg/kg spiking levels, respectively, with acceptable precision. The analytical method was sensitive enough to achieve 0.01-34.3 µg/kg and 0.03-115 µg/kg limits of detection and quantitation, respectively. The scope of the method was demonstrated by analyzing complex solid environmental matrices (chicken manure, swine manure, poultry feed and soil) spiked at 10, 20, 50 and 100 µg/kg levels. The method was also applied for the antibiotic analysis in samples with incurred residues. Different matrices in the order of the magnitude as sediments < poultry feed < swine manure < soil < chicken manure were detected with the residues of fluoroquinolone, macrolide, sulfonamide and tetracycline antibiotics.

Keywords: Antibiotics; Cleanup; Complex solid matrices; Extraction; Liquid chromatography tandem mass spectrometry; Sediments.