Chemometric tools improving the determination of anti-inflammatory and antiepileptic drugs in river and wastewater by solid-phase microextraction and liquid chromatography diode array detection

• Published in: Journal of Chromatography A Vol. 1216; no. 29; pp. 5489 - 5496
• Main Authors: García, M.D. Gil, Cañada, F. Cañada, Culzoni, M.J., Vera-Candioti, L., Siano, G.G., Goicoechea, H.C., Galera, M. Martínez
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 17.07.2009; Amsterdam; New York: Elsevier; Elsevier
• Subjects: Analysis methods; Analytical chemistry; Anti-Inflammatory Agents, Non-Steroidal - analysis; Anticonvulsants - analysis; Applied sciences; Chemistry; Chromatographic methods and physical methods associated with chromatography; Chromatography, Liquid - methods; Exact sciences and technology; Freshwater; Liquid chromatography–diode array detection; Natural water pollution; Other chromatographic methods; Other wastewaters; Pharmaceuticals; Pollution; River water; Second order advantage; Sewage - analysis; Solid Phase Microextraction - methods; Solid-phase microextraction; Wastewater; Wastewaters; Water Pollutants, Chemical - analysis; Water treatment and pollution; Solid-phase microextraction; Liquid chromatography–diode array detection; Second order advantage; Wastewater; River water; Pharmaceuticals; Trace analysis; Chemical analysis; Antiinflammatory agent; Anticonvulsant; Liquid chromatography; Waste water; Chemical enrichment; Solid phase microextraction; Ultraviolet detector; Sample preparation; Surface water; Diode array; Water pollution; Liquid chromatography-diode array detection; Chemometrics; Quantitative analysis
• ISSN: 0021-9673; 1873-3778
• DOI: 10.1016/j.chroma.2009.05.073

An analytical method for the simultaneous determination of seven non-steroidal anti-inflammatory drugs (naproxen, ketoprofen, diclofenac, piroxicam, indomethacin, sulindac and diflunisal) and the anticonvulsant carbamazepine in river and wastewater is reported. The method involves pre-concentration and clean-up by solid-phase microextraction using polydimethylsiloxane/divinylbenzene fibers, followed by liquid chromatography with diode array detection analysis. Owing to the fact that river water samples did not contain interferences and no sensitivity changes due to sample matrix were observed, external calibration was implemented. Standardization was also applied in order to carry out the prediction step by preparing only two diluted standards that were subjected to the pre-concentration step and a set of standards prepared in solvent. For the analysis of wastewater samples, in contrast, it was necessary to implement standard addition calibration in combination with the multivariate curve resolution-alternating least squares (MCR-ALS) algorithm, which allowed us to overcome matrix effect and exploit the second order advantage. Recoveries ranging from 72% to 125% for all pharmaceuticals proved the accuracy of the proposed method in river water samples. On the other hand, wastewater sample recoveries ranged from 83% to 140% for all pharmaceuticals, showing an acceptable performance – considering this sample contains no modeled interferences.