Rapid determination of pharmaceuticals in wastewater by direct infusion HRMS using target and suspect screening analysis

Abstract

A wide-scope screening of active pharmaceutical ingredients (APIs) and their transformation products (TPs) in wastewater can yield valuable insights and pinpoint emerging contaminants that have not been previously reported. Such information is relevant to investigate their occurrence and fate in various environmental compartments. In this study, we explored the applicability of direct infusion high resolution mass spectrometry (DI-HRMS) for comprehensive and rapid detection of APIs and their TPs in wastewater samples. The method was developed using a Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) system and incorporated both wide-scope suspect screening and semi-quantitative determination of selected analytes. The identification strategy was based on the following criteria: narrow accurate mass window (±1.25 ppm) for two most abundant full-MS signals, isotopic pattern fit and additional confirmation on the basis of MS2 spectra at three fragmentation levels. The tentative identification of suspects and target compounds relied on an in-house database containing more than 500 different APIs and TPs. The measured fragment spectra were matched against experimental MS2 patterns obtained from a publicly available spectral library (MassBank of North America) and in-silico generated fragmentation features (from the CFM-ID algorithm). In total, 79 suspects were identified and 24 target compounds were semi-quantified in 72 wastewater samples. The highest detection frequencies in treated wastewater effluents were observed for diclofenac, metoprolol and telmisartan, while hydroxydiclofenac, dextrorphan, and carbamazepine metabolites were the most frequently detected TPs. The obtained API profiles were in accordance with the national consumption statistics and the origin of wastewater samples. The developed method is suitable for rapid screening of APIs in wastewater and can be used as a complementary tool to characterize API emissions from wastewater treatment facilities and to identify problematic compounds that require more rigorous monitoring.