title: Selective determination of pharmaceuticals and illicit drugs in wastewaters using a novel strong cation-exchange solid-phase extraction combined with liquid chromatography-tandem mass spectrometry.
abstract: In this study, two materials are presented with strong cation-exchange (SCX) behaviour synthesised by two different approaches and then crushed for their application as sorbents for solid-phase extraction (SPE) to extract a group of pharmaceuticals and illicit drugs selectively from wastewater samples. The first SCX polymer was obtained by copolymerisation of three monomers: 2-acrylamido-2-methylpropane sulphonic acid (AMPSA), 2-hydroxyethyl methacrylate (HEMA) and pentaerythritol triacrylate (PETRA), while the second was obtained by post-modification with sulphuric acid (H2SO4) of a copolymer based on HEMA and divinylbenzene (DVB). After their syntheses, both polymers were evaluated as SPE sorbents, with all parameters affecting SPE being optimised, such as sample pH, washing and elution solvents and volumes. Thanks to the sulphonic groups present in the structure of the polymers, all of the compounds with basic functionalities were retained on the sorbents after the washing step, removing the acidic analytes and other interfering compounds, providing successful results in terms of ion suppression/enhancement (-12% and 21%) when wastewater samples were analysed. However, AMPSA/HEMA/PETRA (20/60/20) failed to retain the analytes after loading wastewater samples (25 or 50mL), decreasing analyte recovery values significantly, whereas the sulphonated HEMA/DVB (50/50) enabled good SPE performance with recovery values between 70% and 98%, except for ranitidine and EDDP (39% and 43%, respectively). Therefore, this polymer was selected for further method validation and quantification of wastewater samples, providing low method detection limits (MDLs) in this matrix (from 2 to 40ngL(-1)). Finally, most of the studied compounds were detected and quantified in wastewater samples, especially atenolol, ranitidine, cocaine and its metabolite benzoylecgonine.
authors.affiliation: Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, Campus Sescelades Marcel·lí Domingo, s/n, 43007 Tarragona, Spain. Electronic address: nuria.gilart@urv.cat.
authors.forename: Núria
authors.initials: N
authors.lastname: Gilart
authors.affiliation: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL Scotland, UK.
authors.forename: P A G
authors.initials: PA
authors.lastname: Cormack
authors.affiliation: Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, Campus Sescelades Marcel·lí Domingo, s/n, 43007 Tarragona, Spain.
authors.forename: Rosa Maria
authors.initials: RM
authors.lastname: Marcé
authors.affiliation: Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, Campus Sescelades Marcel·lí Domingo, s/n, 43007 Tarragona, Spain. Electronic address: nuria.fontanals@urv.cat.
authors.forename: Núria
authors.initials: N
authors.lastname: Fontanals
authors.affiliation: Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, Campus Sescelades Marcel·lí Domingo, s/n, 43007 Tarragona, Spain.
authors.forename: Francesc
authors.initials: F
authors.lastname: Borrull
mesh_terms: D002412:Cations / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D013287:Illicit Drugs / Q000032:analysis* / Q000737:chemistry; D057230:Limit of Detection; D052616:Solid Phase Extraction / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000379:methods*; D062065:Wastewater / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000032:analysis* / Q000737:chemistry
chemical_list: D002412:Cations; D013287:Illicit Drugs; D062065:Wastewater; D014874:Water Pollutants, Chemical
keywords: Mixed-mode solid-phase extraction; Pharmaceuticals and illicit drugs; Selectivity; Strong cation-exchange; Wastewaters