Automated method to determine pharmaceutical compounds in wastewater using on-line solid-phase extraction coupled to LC-MS/MS

Abstract

An automated method was developed using on-line solid-phase extraction (SPE) as a sample preparation step, coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS), for determination of pharmaceutical compounds in wastewater samples at nanograms per liter to micrograms per liter concentration levels. This method is suitable for use in routine analysis, especially in environmental applications, avoiding cross-contamination and requiring minimal sample handling. Results can be obtained rapidly, with a chromatographic run time of only 24 min (including sample preparation and chromatographic analysis). Using a 50 μL injection volume, the method was validated according to international guidelines, considering parameters included in terms of method detection (MDL) and quantification limit (MQL), linearity, inter-day and intra-day precisions, and matrix effects. Assessment of chromatographic efficiency considered peak resolution and asymmetry, and carryover was evaluated to ensure analytical reliability and the ability to reuse the SPE cartridge. The intra- and inter-day precisions were lower than 10 and 17%, respectively. The MDL values ranged from 1×10^-6 to 1 μg L^-1, while the MQL values were from 0.001 to 3 μg L^-1. Matrix effects were minimized by isotope dilution calibration. Application of the method to 20 wastewater samples showed that caffeine was the most frequently detected compound, with the highest concentration of 715 μg L^-1, while other pharmaceutical compounds were detected in fewer samples and at lower concentrations (up to 8.51 μg L^-1).

Keywords: Emerging contaminants; Liquid chromatography-tandem mass spectrometry; On-line sample preparation; Pharmaceutical compounds; Wastewater analysis.