Coupling of solid‐phase microextraction with micellar desorption and high performance liquid chromatography for the determination of pharmaceutical residues in environmental liquid samples

Abstract

A residue analytical method combining solid-phase microextraction (SPME) with external micellar desorption (MD) and high-performance liquid chromatography with diode array detector (HPLC-DAD) has been developed and validated for the simultaneous determination of six pharmaceutical compounds, belonging to various therapeutic categories in water samples. Target compounds include antiinflamatory drugs (ibuprofen, ketoprofen and naproxen), an analgesic (phenazone), a lipid regulator (bezafibrate) and an antiepileptic (carbamazepine). A detailed study of the experimental conditions of extraction and desorption with different surfactants was performed in order to obtain the best results during instrumental analysis. Of the different fibers and surfactants investigated, 65 microm polydimethysiloxane-divinilbenzene (PDMS-DVB) fiber and polyoxyethylene 10 lauryl ether (POLE) and polyoxyethylene 6 lauryl ether (C(12)E(6)) as desorbing agents produced the optimal response to pharmaceutical residues. Recoveries obtained were generally higher than 80% and the variability of the method was below 16% for all compounds in both surfactants. Method detection limits were 0.05-12 ng mL(-1) for POLE and 0.1-5 ng mL(-1) for C(12)E(6). The developed method was compared using external desorption with organic solvent and it was successfully applied to the determination of these pharmaceutical compounds in water samples from different origin. Solid-phase microextraction with micellar desorption (SPME-MD) represents a new approach for the extraction of different pharmaceutical compounds in natural waters because it combines shorter handling time, better efficiency, safety and more environmentally friendly process than the traditional methods.

Development of a New Microextraction Fiber Combined to On-Line Sample Stacking Capillary Electrophoresis UV Detection for Acidic Drugs Determination in Real Water Samples

“…Moreover, the precision of the method ( Table 5 ) is in agreement with values reported in the literature when working with SPME [ 11 , 17 , 20 , 21 , 23 , 26 , 27 ]. Likewise, comparing to previously developed methods coupling off-line SPME to CZE analysis, the intra-day reproducibility (approximately 10%) of the new proposed method herein, is not significantly different [ 19 , 43 , 44 ].…”

“…Likewise, comparing to previously developed methods coupling off-line SPME to CZE analysis, the intra-day reproducibility (approximately 10%) of the new proposed method herein, is not significantly different [ 19 , 43 , 44 ]. It is worth noticing that such intra-day reproducibility values are also consistent with other coupled methods, i.e., SPME-HPLC or SPME-GC [ 20 , 21 , 23 ].…”

“…However, it has certain requirements that are not so attractive to researchers, such as high cost, fragility and limited lifetime of commercial fibers due to the experimental conditions, as they tend to degrade as they are used. These drawbacks have led to the development of various technologies and techniques in order to prepare laboratory-made fibers, but most of the procedures are complicated and time consuming [ 9 , 11 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 ].…”

“…Furthermore, SPME was used as an off-line preconcentration technique for the analysis of acidic drugs coupled to HPLC and GC in order to lower their limits of detection and quantification in complex environmental samples [ 7 , 9 , 20 , 21 , 22 , 23 ]. Herein, we propose to develop a non-commercial SPME fiber for the off-line purification and preconcentration of acidic drugs in water samples coupled to an on-line ACN stacking CE-DAD analysis.…”

Mixed Matrix Membrane Tip Extraction Coupled with UPLC–MS/MS for the Monitoring of Nonsteroidal Anti-Inflammatory Drugs in Water Samples

“…Miniaturized membrane-based microextraction techniques have been proposed for the extraction of NSAIDs and organic pollutants from various matrices. For instance, hollow-fiber liquid-phase microextraction (HF-LPME) [21], electromembrane extraction (EME) [22][23][24][25] and SPME [26] are proven to be beneficial in minimizing organic solvent usage. Nevertheless, analyzing the trace organic compound remains complex in complicated matrices and a wide range of chemical properties of the analytes, and they can be at concentrations as low as pg/mL in range [27,28].…”