Simultaneous determination of corticosteroids, androgens, and progesterone in river water by liquid chromatography–tandem mass spectrometry

The assessment of steroidal hormones in the environment requires sensitive and selective analytical techniques suitable for sample matrices. This paper reports a simple method to analyze simultaneously six corticosteroids (triamcinolone, cortisol, dexamethasone, flumethasone, prednisolone, triamcinolone acetonide), four androgens (boldenone, epitestosterone, methyltestosterone, nortestosterone), and progesterone in river and drinking water sources. The developed method is based on a single solid-phase extraction (SPE) followed by liquid chromatography/tandem mass spectrometry (LC–MS/MS) with atmospheric pressure chemical ionization (APCI). The main advantage of this method over other methods includes the use of a single SPE with a low volume cartridge for sample preparation, separation of steroids on alkyl-amide stationary phase with no matrix interferences by LC–MS/MS analysis, and simultaneous analysis of more than two groups of steroids. The method was characterized by generally good performance, analyzing three groups of steroids using 100 and 1000 mL samples with average recovery ranges of 80–109% and 68–126%, respectively at a level of 1 ng L−1. The limit of detection (LOD) ranged from 0.06 to 0.2 and 0.01–0.21 ng L−1 for 100 mL and 1000 mL samples volumes, respectively. Sixty samples of Danube River and drinking water sources from different regions of Hungary were collected to analyze target steroids in two sampling periods in 2008 and 2009. Steroids, except cortisol, dexamethasone, flumethasone, prednisolone, epitestosterone and progesterone were below detection limits. Endogenous steroids (cortisol, epitestosterone, progesterone) were present in the concentration range of 0.08–2.67 ng L−1 while synthetic corticosteroids (dexamethasone, flumethasone, and prednisolone) varied from 0.064 to 1.43 ng L−1. Steroids were present in river water, except progesterone, which was present only in ground water. Levels of steroids are compared with other rivers in the world and were briefly discussed.