Multiresidue analysis of 88 polar organic micropollutants in ground, surface and wastewater using online mixed-bed multilayer solid-phase extraction coupled to high performance liquid chromatography–tandem mass spectrometry

An automated multiresidue method consisting of an online solid-phase extraction step coupled to a high performance liquid chromatography–tandem mass spectrometer (online-SPE–HPLC–MS/MS method) was developed for the determination of 88 polar organic micropollutants with a broad range of physicochemical properties (log DOW (pH 7): −4.2 to 4.2). Based on theoretical considerations, a single mixed-bed multilayer cartridge containing four different extraction materials was composed for the automated enrichment of water samples. This allowed the simultaneous analysis of pesticides, biocides, pharmaceuticals, corrosion inhibitors, many of their transformation products, and the artificial sweetener sucralose in three matrices groundwater, surface water, and wastewater. Limits of quantification (LOQs) were in the environmentally relevant concentration range of 0.1–87 ng/L for groundwater and surface water, and 1.5–206 ng/L for wastewater. The majority of the compounds could be quantified below 10 ng/L in groundwater (82%) and surface water (80%) and below 100 ng/L in wastewater (80%). Relative recoveries were largely between 80 and 120%. Intraday and inter-day precision, expressed as relative standard deviation, were generally better than 10% and 20%, respectively. 50 isotope labeled internal standards were used for quantification and accordingly, relative recoveries as well as intraday and inter-day precision were better for compounds with corresponding internal standard. The applicability of this method was shown during a sampling campaign at a riverbank filtration site for drinking water production with travel times of up to 5 days. 36 substances of all compound classes investigated could be found in concentrations between 0.1 and 600 ng/L. The results revealed the persistence of carbamazepine and sucralose in the groundwater aquifer as well as degradation of the metamizole metabolite 4-acetamidoantipyrine.

► We developed a new online-SPE–HPLC–MS/MS method for polar organic micropollutants. ► Four different SPE materials were combined in one multiple use enrichment cartridge. ► 88 compounds of different classes and physicochemical properties are included. ► LOQs, recoveries and precision were good for ground, surface and wastewater. ► The method was applied during a field campaign at a riverbank filtration site.