Determination of drugs in surface water and wastewater samples by liquid chromatography–mass spectrometry: methods and preliminary results including toxicity studies with Vibrio fischeri

• Published in: Journal of Chromatography A 2001-12, Vol.938 (1), p.187-197
• Main Authors: Farré, Marinel·la, Ferrer, Imma, Ginebreda, Antoni, Figueras, Mercè, Olivella, Lourdes, Tirapu, Lluis, Vilanova, Manel, Barceló, Damià
• Format: Article
• Language: English
• Subjects: Analysis methods; Animal, plant and microbial ecology; Applied ecology; Applied sciences; Biological and medical sciences; Chromatography, Liquid - methods; Diclofenac; Drugs; Ecotoxicology, biological effects of pollution; Exact sciences and technology; Fundamental and applied biological sciences. Psychology; Gemfibrozil; Ibuprofen; Industrial Waste; Ketoprofen; Naproxen; Natural water pollution; Other wastewaters; Pharmaceutical Preparations - analysis; Pollution; Salicylic acid; Spectrometry, Mass, Electrospray Ionization - methods; Techniques; Toxicity Tests; Vibrio - drug effects; Vibrio fischeri; Wastewaters; Water Pollutants, Chemical - analysis; Water treatment and pollution
• ISSN: 0021-9673
• DOI: 10.1016/S0021-9673(01)01154-2

In the present work a combined analytical method involving toxicity and liquid chromatography–electrospray ionization-mass spectrometry (LC–ESI-MS) was developed for the determination of pharmaceutical compounds in water samples. The drugs investigated were the analgesics: ibuprofen, ketoprofen, naproxen, and diclofenac, the decomposition product of the acetyl salicylic acid: salicylic acid and one lipid lowering agent, gemfibrozil. The selected compounds are acidic substances, very polar and all of them are analgesic compounds that can be purchased without medical prescription. The developed protocol consisted, first of all, on the use Microtox ® and ToxAlert ®100 toxicity tests with Vibrio fischeri for the different pharmaceutical drugs. The 50% effective concentration (EC 50) values and the toxicity units (TU) were determined for every compound using both systems. Sample enrichment of water samples was achieved by solid-phase extraction procedure (SPE), using the Merck LiChrolut ® EN cartridges followed by LC–ESI-MS. Average recoveries loading 1 l of samples with pH=2 varied from 69 to 91% and the detection limits in the range of 15–56 ng/l. The developed method was applied to real samples from wastewater and surface-river waters of Catalonia (north-east of Spain). One batch of samples was analyzed in parallel also by High Resolution Gas Chromatography coupled with Mass Spectrometry (HRGC–MS) and the results have been compared with the LC–ESI-MS method developed in this work.