Cleanup strategies and advantages in the determination of several therapeutic classes of pharmaceuticals in wastewater samples by SPE–LC–MS/MS

Abstract

This work describes the development and validation of an offline solid-phase extraction with simultaneous cleanup capability, followed by liquid chromatography-(electrospray ionisation)-ion trap mass spectrometry, enabling the concurrent determination of 23 pharmaceuticals of diverse chemical nature, among the most consumed in Portugal, in wastewater samples. Several cleanup strategies, exploiting the physical and chemical properties of the analytes vs. interferences, alongside with the use of internal standards, were assayed in order to minimise the influence of matrix components in the ionisation efficiency of target analytes. After testing all combinations of adsorbents (normal-phase, ion exchange and mixed composition) and elution solvents, the best results were achieved with the mixed-anion exchange Oasis MAX cartridges. They provided recovery rates generally higher than 60%. The precision of the method ranged from 2% to 18% and 4% to 19% (except for diclofenac (22%) and simvastatin (26%)) for intra- and inter-day analysis, respectively. Method detection limits varied between 1 and 20 ng L(-1), while method quantification limits were <85 ng L(-1) (both excluding ibuprofen). This analytical method was applied to gather preliminary results on influents and effluents of two wastewater treatment plants (WWTPs) located in the urban region of Porto (Portugal). Typically, paracetamol, hydrochlorothiazide, furosemide, naproxen, ibuprofen, diclofenac and bezafibrate were detected in concentrations ranging from 1 to 20 μg L(-1), while gemfibrozil, simvastatin, ketoprofen, azithromycin, bisoprolol, lorazepam and paroxetine were quantified in levels below 1 μg L(-1). These WWTPs were given particular attention since they discharge their effluents into the Douro river, where water is extracted for the production of drinking water. Some sampling spots in this river were also analysed.

Determination of selected cardiovascular active compounds in environmental aquatic samples – Methods and results, a review of global publications from the last 10 years

“…It is designed for the extraction of basic and neutral compounds. Oasis MAX and Strata-A are in contrast anion exchangers (quaternary amine) also built on mix mode polymeric sorbent (Sousa et al, 2011). Thus they are optimized for the extraction of acidic compounds with anion exchange groups, and also for neutral compounds which will be retained on the polymeric sorbent.…”

“…In the past decade, pharmaceuticals have become an attractive field for research under environmental studies (Kasprzyk-Hordern et al, 2008;Santos et al, 2009;Gros et al, 2010;Sousa et al, 2011;Gracia-Lor et al, 2012). This is mainly due to the increased consumption of drugs worldwide, demographic changes and observed medicinal development progress (Hughes et al, 2013).…”

Response surface methodology applied to SPE for the determination of ibuprofen in various types of water samples

“…Most SPE methods in the literature reported the use of 50 [24,25], 100 [24,[26][27][28], 150 [29], 200 [27,28], 250 [30], . A1-Oasis R HLB (RSD = 1.6%), A2-Lichrolut EN/RP-18 (RSD = 1.3%), A3-Lichrolut EN (RSD = 9.2%), A4-StrataTM-X (RSD = 3.8%), A5-StrataTM-SDB-L (RSD = 3.1%), A6-StrataTM-C18-E (RSD = 7.9%), A7-ChromabondR HR-X (RSD = 17%), and A8-ChromabondR C18ec (RSD = 4.1%).…”

Proteomic changes in Corbicula fluminea exposed to wastewater from a psychiatric hospital

“…One of the major sources of pharmaceutical compounds to the environment is wastewater treatment plants (WWTPs) where their elimination is incomplete and the efficiency of removal depends on the type of treatment (Calisto and Esteves 2009;Yuan et al 2013), amount used, as well as pharmacokinetic and physicochemical properties of the drugs (Brooks et al 2005). Several studies documented the occurrence and concentrations of pharmaceuticals including the persistence of psychiatric drugs which are among the pharmaceuticals most frequently detected in the aquatic environment (Fong and Ford 2014) in various aquatic systems (Roberts and Thomas 2006;Bartelt-Hunt et al 2009;Gonzales et al 2010;Bouissou-Schurtz et al 2014) and in conventional WWTPs (Calisto and Esteves 2009;Santos et al 2010;Sousa et al 2011). These levels range from ng to μg.L −1 (Deblonde et al 2011;Orias and Perrodin 2014;Pasquini et al 2014), and the amount detected in fresh and ground waters as well as in sediments and biota depend on the quantity used and their chemical composition (Heberer 2002).…”