Low-temperature partitioning extraction followed by liquid chromatography tandem mass spectrometry determination of multiclass antibiotics in solid and soluble wastewater fractions.

An analytical method based on low-temperature partitioning extraction (LTPE) followed by high performance liquid chromatography coupled to triple quadrupole mass spectrometry analysis was developed and validated for the determination of eight multiclass antibiotics in wastewater. The analyzed target antibiotics included one β-lactam, two sulfonamides, three fluoroquinolones, one macrolide and one diaminopyrimidine. LTPE parameters such as sample pH, volume ratio between sample and extractor solvent, ultra-sonic extraction time, extraction tube material, solvent and volume to reconstitute the sample extracts, were optimized. Additionally, the influence of solids on extraction efficiency was evaluated. Quantification of the target antibiotics was performed by double consecutive injection method, without the use of a labeled compound, in order to correct matrix effects. The whole samples were analyzed, including, liquid and solid fractions of wastewater. The results revealed that the filtration step can underestimate the total antibiotics concentration, particularly to the hydrophobic compounds that have higher affinity for solids, indicating that the suspended wastewater particulate should not be neglected. The method detection limit ranged from 18.54 ng L (trimethoprim) to 78.49 ng L (ciprofloxacin). Intra-day precision of less than 12.3% was achieved. The recoveries values ranged from 13.9% (sulfadiazine) to 48.9% (erythromycin) in influent samples and from 19.1% (sulfadiazine) to 57.2% (ciprofloxacin) in effluent samples. The method was applied to the measurement of antibiotic residues in influent and effluent from wastewater treatment plants. The majority target antibiotics were detected in wastewater samples. Their concentrations ranged from 237 to 9553 ng L in influent and from 212 to 1660 ng L in effluent. This work provides new insights on the applicability of LTPE for antibiotic residues extraction from wastewater. In addition, the performed analysis highlights the importance of measuring total concentrations of analytes in whole sample.