Analysis of 100 pharmaceuticals and their degradates in water samples by liquid chromatography/quadrupole time-of-flight mass spectrometry

A straightforward methodology for the chromatographic separation and accurate mass identification of 100 pharmaceuticals including some of their degradation products was developed using liquid chromatography/quadrupole time-of-flight mass spectrometry (LC/Q-TOF-MS). A table compiling the protonated or deprotonated exact masses for all compounds, as well as the exact mass of several fragment ions obtained by MS–MS is included. Excellent chromatographic separation was achieved by using 3.5 μm particle size columns and a slow and generic 30-min gradient. Isobaric and isomeric compounds (same nominal mass and same exact mass, respectively) were distinguished by various methods, including chromatography separation, MS–MS fragmentation, and isotopic signal identification. Method reporting limits of detection ranged from 1 to 1000 ng/L, after solid-phase extraction of 100 mL aqueous samples. The methodology was successfully applied to the analysis of surface water impacted by wastewater effluent by identifying many of the pharmaceuticals and metabolites included in the list. Examples are given for some of the most unusual findings in environmental samples. This paper is meant to serve as a guide for those doing analysis of pharmaceuticals in environmental samples, by providing exact mass measurements of several well known, as well as newly identified and environmentally relevant pharmaceuticals in water samples.

► Exact masses and fragment ions of 100 pharmaceuticals by LC/Q-TOF-MS. ► Use of resolving power for discrimination of isobaric/isomeric compounds. ► Fragmentation patterns shown for some pharmaceuticals by accurate mass. ► Relevant environmental findings after analysis of surface water samples.