High-performance liquid chromatography quadrupole time-of-flight mass spectrometry method for the analysis of antidiabetic drugs in aqueous environmental samples

Antidiabetic compounds are among the most prescribed pharmaceuticals. Nevertheless, their presence in the environment has been scarcely evaluated as there is no method for their determination in environmental samples. This paper reports the development of an analytical method for the determination of traditionally used antidiabetics (metformin and glibenclamide) and novel antidiabetics (vildagliptin, sitagliptin and pioglitazone). The method is based on solid-phase extraction and determination by high-performance liquid chromatography quadrupole time-of-flight mass spectrometry. The method was applied to effluent wastewater, river water and tap water. Mean recoveries of glibenclamide, vildagliptin, sitagliptin and pioglitazone in the matrices evaluated were in the range 78–83%; limits of quantification were in the range 0.4–4.3 ng L−1; and precision values were in the range 2.2–13%. The high hydrophilicity and polarity of metformin complicated its simultaneous extraction. Chromabond Tetracycline cartridges and sample pH 8.5 were applied to the extraction of glibenclamide, vildagliptin, sitagliptin and pioglitazone. Oasis HLB cartridges, neutral sample pH and SDS as ion-pair reagent were used for the extraction of metformin. Validation results of metformin were not as favorable as those of the other antidiabetic drugs but were comparable with others previously reported. The developed method was applied to the first-time determination of the concentrations of the five antidiabetic drugs in wastewater, river water and tap water. Metformin was the antidiabetic drug at the highest concentration in wastewater and surface water (up to 253 ng L−1 and 104 ng L−1, respectively). Two of the antidiabetic drugs of recent prescription, sitagliptin and vildagliptin, were found in effluent wastewater at concentrations of 117 ng L−1 and 12 ng L−1, respectively, and in river water at concentrations of 35 ng L−1 and 6 ng L−1, respectively, whereas the classic antidiabetic drug glibenclamide and the novel drug pioglitazone were not detected.

► Determination of metformin by reverse-phase chromatography.
► Chromatographic determination of metformin and four novel antidiabetic drugs.
► Applicability to wastewater, river water and tap water tested.
► Metformin, sitagliptin and vildagliptin detected in wastewater and river water.