A method has been developed for the trace analysis of 15 pharmaceuticals, four metabolites of pharmaceuticals, three potential endocrine disruptors, and one personal care product in various waters. The method employs solidphase extraction (SPE) and liquid chromatography/tandem mass spectrometry (LC-MS/MS), using electrospray ionization (ESI) in both positive and negative modes. Unlike many previous LC-MS/MS methods, which suffer from matrix suppression, this method uses isotope dilution for each compound to correct for matrix suppression, as well as SPE losses and instrument variability. The method was tested in five matrices, and results indicate that the method is very robust. Matrix spike recoveries for all compounds were between 88 and 106% for wastewater influent, 85 and 108% for wastewater effluent, 72 and 105% for surface water impacted by wastewater, 96 and 113% for surface water, and 91 and 116% for drinking water. The method reporting limits for all compounds were between 0.25 and 1.0 ng/L, based on 500 mL of sample extracted and a final extract volume of 500 µL. Occurrence of the compounds in all five matrices is also reported.
IntroductionDue to a number of recent reports (1-7), sustained interest in the presence and fate of organic contaminants has been thoroughly established. As concern regarding the environmental impact of exogenous chemicals present in water continues to grow, so too have the number of analytical methods dedicated to their identification and quantification (8,9). This is especially true for the analysis of these compounds by liquid chromatography-mass spectrometry (LC-MS) (10-12). However, even though the number of methods using LC-MS has risen dramatically, discussion of matrix suppression and enhancement that can occur during the use of LC-MS for environmental analysis and the effect it can have on quantification accuracy and precision has been discussed in a relatively small number of publications.Although the cause of matrix effects has been postulated to be natural organic matter (13), the mechanism still has not been fully resolved (14). Regardless, recent reports have shown drastic matrix effects when using LC-MS for the analysis of environmental and biological samples (14-21). There have been a number of methods proposed to compensate for matrix effects by using different calibration techniques, including standard addition (13, 17, 22), surrogate monitoring (15, 20), and various forms of internal calibration (14-16, 19, 23). Still more have been developed to minimize matrix effects using different extraction, cleanup and elution techniques, including size-exclusion chromatography (18,24), solid-phase extraction (22), LC chromatographic procedures (14,22), ultra performance liquid chromatography (25), hollow fiber liquid-phase microextraction (26), flowsplitting and reduced eluent flow rates (24,27). However, most become problematic when applied to the simultaneous analysis of a broad range of compounds that encompass many different classes and structures in matrices havi...