Evaluation of mixed mode solid phase extraction cartridges for the preconcentration of beta-lactam antibiotics in wastewater using liquid chromatography with UV-DAD detection

Abstract

A novel and simple method has been developed for the simultaneous determination of beta-lactam antibiotics (BLAs) (penicillin G, amoxicillin, ampicillin, penicillin V, oxacillin, cloxacillin, dicloxacillin and nafcillin) in wastewater. The method is based on solid-phase extraction (SPE) and high performance liquid chromatography with UV-diode array detection (UV-DAD). Two SPE cartridges have been compared for sample clean up and preconcentration: a reversed-phase silica-based cartridge (Bond Elut C 18, Varian Inc.) and a strong polymeric mixed mode anion exchanger (Oasis MAX, Waters). The penicillins have been separated using a LUNA™ C 18 (2) (150 mm × 4.6 mm, 5 μm) HPLC column and gradient elution with mobile phases consisting of aqueous trifluoroacetic acid and acetonitrile. The analytical wavelength was set at 220 nm. Under optimised conditions it was possible to preconcentrate up to 1000 mL of Milli-Q water in the Oasis MAX cartridges with recoveries in the range 82–97% (R.S.D. 2–9%) for all the antibiotic tested, except amoxicillin (52%, R.S.D. 8%), and limits of detection in the range of 8–24 ng L −1. The matrix components in industrial and urban wastewater samples reduce the preconcentration efficiency in both sorbents, especially for the Bond Elut C 18. The use of the Oasis MAX allowed detection limits between 2.9–25.6, 2.5–12.4 and 2.2–12.7 μg L −1, when processing 250 mL of industrial, influent and effluent sewage treatment plant (STP) samples. Recoveries ranged between 46–91, 28–91 and 39–114% (industrial, influent and effluent STP, respectively) for samples spiked with all the antibiotics at 25 and 75 μg L −1 ( n = 3 for each level).