Selective determination of antimycotic drugs in environmental water samples by mixed-mode solid-phase extraction and liquid chromatography quadrupole time-of-flight mass spectrometry.

The suitability of mixed-mode (reversed-phase and cationic exchange) solid-phase extraction (SPE) for the selective concentration of basic antimycotic drugs (belonging to triazole, imidazole and allylamine chemical classes) in environmental water samples has been demonstrated for first time. The use of a sequential elution protocol, allowing the removal of neutral and acidic interferences before analytes extraction, led to a significant reduction of matrix effects, during electrospray ionization (ESI), in comparison with results reported for reversed-phase sorbents. In combination with liquid chromatography (LC) quadrupole time-of-flight (QTOF) mass spectrometry (MS) determination, the developed method attained limits of quantification (LOQs) comprised between 2 and 15ngL(-1). After internal surrogate correction, accurate results (in most cases, recoveries ranged between 75 and 117%) were obtained for spiked aliquots of raw and treated wastewater, as well as river water, using quantification against calibration standard solutions in methanol (2% in NH3). Accurate, scan MS/MS spectra allowed the unambiguous identification of target compounds in environmental samples; furthermore, the information contained in MS spectra was used for the screening of additional antimycotics in the processed samples. Fluconazole, ketoconazole, miconazole and clotrimazole were measured in wastewater samples at concentrations up to 200ngL(-1). The screening capabilities of the LC-QTOF-MS system permitted to identify the systematic presence of climbazole in the processed samples.