Solid-phase extraction and fractionation of multiclass pollutants from wastewater followed by liquid chromatography tandem-mass spectrometry analysis

Herein, we describe a modular solid-phase extraction (SPE) setup, combining three sorbents, for the effective extraction of neutrals, acidic, and basic micropollutants from wastewater, followed by their further elution in three independent extracts. The performance of this approach was demonstrated for a suite of 64 compounds, corresponding to different chemical families, using liquid chromatography tandem-mass spectrometry (LC–MS/MS). Target compounds were effectively extracted from wastewater samples; moreover, 62 out of 64 species were isolated in just one of the three fractions (neutrals, acids, and bases) obtained from the combination of sorbents. Globally, the efficiency and the selectivity of the SPE methodology improved the features obtained using generic SPE polymers, displaying just reversed-phase interactions. The overall recoveries of the analytical method, calculated against solvent-based calibration standards, stayed between 80 and 120% for 57 and 60 compounds, in raw and treated wastewater, respectively. Procedural limits of quantification (LOQs) varied from 1 to 20 ng L(−1). Analysis of urban wastewater samples identified a group of 19 pollutants showing either negligible median removal efficiencies (± 20%) during wastewater treatment, or even a noticeable enhancement (case of the biodegradation product of the drug valsartan), which might be useful as markers of wastewater discharges in the aquatic environment. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s00216-022-04066-8.