Validation and uncertainty estimation of a multiresidue method for pharmaceuticals in surface and treated waters by liquid chromatography–tandem mass spectrometry

The estimation of measurement uncertainty associated with quantitative results is essential to assure the reliability of analytical methods and mandatory when a laboratory implements ISO standard 17025. In this work, a quantitative multi-residue method based on solid-phase extraction (SPE) and ultra-performance liquid chromatography tandem mass spectrometry detection (LC–MS/MS) has been developed and validated for the analysis of 53 pharmaceuticals (analgesics, anti-inflammatories, antibiotics, lipid regulating agents, cholesterol lowering stating agents, gastric drugs, X-ray, and miscellaneous compounds such as sildenafil, prednisone, triclosan, chlorhexidine and miconazole) in surface and drinking waters. A full validation of the method, according to ISO standard 17025 procedure, was performed. Linearity (0.01–250 ng/L range), intra-day precision (3–19%RSD in surface water and 2–19%RSD in drinking water) and inter-day precision (3–16%RSD in surface water and 1–18%RSD in drinking water), matrix effects (low matrix effects were observed for 50% of compounds in both matrices), limits of quantification (0.2–40 ng/L in surface water and 0.2–30 ng/L in drinking water) were calculated. The recoveries at 100 ng/L were >80% for 72% and 79% of the target compounds in surface and drinking waters, respectively. The information obtained from the full method validation has been used to estimate the expanded uncertainty and the uncertainties contributions of the different individual steps of the method for the determination of pharmaceuticals at trace levels in waters. Expanded relative uncertainties ranged from 6% to 23% being the uncertainty associated with reproducibility the main contribution.

► A new multiresidue SPE-LC–MS/MS method to analyze pharmaceuticals in water was validated.
► The expanded relative uncertainties in surface and drinking waters were calculated.
► Surface and treated water samples have been analyzed in a seasonal study.
► Results proved the suitability of the treatment in the drinking water plant.