A Rapid Analytical Approach for Monitoring Pharmaceuticals in Hospital Wastewater—A DPX-Based Procedure with Environmentally-Friendly Extraction Phase Coupled to High Performance Liquid Chromatography–Diode Array/Fluorescence Detectors

Abstract

In this study, a novel analytical methodology based on disposable pipette extraction (DPX) was developed using an alternative extraction phase for the extraction/determination of six pharmaceutical compounds, including carbamazepine, diclofenac, naproxen, fluoxetine, losartan and 17α-ethinylestradiol, in samples of hospital wastewater by high-performance liquid chromatography coupled to diode array and fluorescence detectors. The performance of three extraction phases was examined, including 3-n-propyl (3-methylpyridinium) silsesquioxane chloride (Si3Py+Cl−), the conductive polymer polypyrrole (PPy), and polypyrrole modified with cetyltrimethylammonium bromide (PPy.CTAB). The optimization of the experimental parameters was performed through univariate and multivariate approaches. The optimized condition was obtained with the use of 20 mg of Si3Py+Cl− as extraction phase; six extraction cycles with 700 μL of sample in each cycle and 15 s of extraction time; three desorption cycles with 100 μL of ACN (same aliquot) and 15 s of desorption time; and sample pH adjusted at 3.5 and addition of 15% (w/v) of NaCl in the sample. The methodology proposed exhibited environmentally-friendly aspects with a significantly reduced volume of organic solvent (only 100 µL) and a small amount of extraction phase (20 mg). In addition, the extraction phase employed exhibits a simple synthetic procedure, low cost, and high stability in organic solvent. Moreover, the method developed exhibits high throughput (extraction time of 6.5 min per sample), and robustness. The analytical figures of merit were obtained using hospital wastewater, and the values were very satisfactory. The correlation coefficients were higher than 0.9710. LODs and LOQs ranged from 0.030 µg L−1 to 1.510 µg L−1 and 0.10 µg L−1 to 5.00 µg L−1, respectively. Relative recoveries varied from 80 to 127%, and intra-day (n = 3) and inter-day (n = 9) precision was lower than 19%.