Comprehensive Target Analysis for 484 Organic Micropollutants in Environmental Waters by the Combination of Tandem Solid-Phase Extraction and Quadrupole Time-of-Flight Mass Spectrometry with Sequential Window Acquisition of All Theoretical Fragment-Ion Spectra Acquisition.

There are many thousands of chemicals in use for a wide range of purposes, and highly efficient analytical methods are required to monitor them for protection of the environment. In order to cope with this difficult task we developed a novel, comprehensive method for 484 substances in water samples. In this method target chemicals were extracted by tandem SPE and then determined by LC-QTOF-MS-SWATH. Targets were unambiguously identified using retention times, accurate masses of a precursor and two product ions, their ion ratios, and accurate MS/MS spectrum. Quantitation was achieved by the internal standard method using a precursor ion. Results of recovery tests at two concentrations (50 and 500 ng L) showed average recoveries of 87.5% and 87.0% (RSD, 9.1% and 9.4%), respectively. Limits of detection of one-half of the targets were below 1.0 ng L. The method was applied to the influent and effluent of a sewage treatment plant, and around 100 chemicals were detected. Results of examination on matrix effects using their extracts spiked with 209 pesticides showed that the ratios of detected amounts between the extracts and the standard solution were 89.8% (influent) and 91.7% (effluent), respectively. In addition, investigation on the stability of calibration curves by injecting the same standards for 1 year showed that their quantitative results did not change; average accuracy was 103.3% (RSD, 10.0%), indicating that the calibration curves can be used for an extended period of time without calibration, and quantitative retrospective analysis can be done after creating calibration curves for new targets.