title: Comparison of electrospray ionization, atmospheric pressure chemical ionization and atmospheric pressure photoionization for determining estrogenic chemicals in water by liquid chromatography tandem mass spectrometry with chemical derivatizations.
abstract: This study compared the sensitivities and matrix effects of four ionization modes and four reversed-phase liquid chromatographic (LC) systems on analyzing estrone (E1), 17beta-estradiol (E2), estriol (E3), 17alpha-ethinylestradiol (EE2), 4-nonylphenol (NP), 4-tert-octylphenol (OP), bisphenol A (BPA) and their derivatives of dansyl chloride or pentafluorobenzyl bromide (PFBBr) in water matrixes using a triple-quadrupole mass spectrometer with selected reaction monitoring (SRM). The four probes were electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI) and APCI/APPI; the four LC systems were ultra-performance liquid chromatography (UPLC) with or without post-column split, a mixed-mode column and two-dimensional LC (2D-LC). Dansylated compounds with ESI at UPLC condition had the most intense signals and less matrix effects of the various combinations of ionization and LC systems. The on-column limits of detection (LODs) of dansylated estrogens by SRM were 0.05-0.20 pg, and the LODs in sewage treatment plant effluent and in river water were 0.23-0.52 and 0.56-0.91 ng/L, respectively. The LODs using selected ion monitoring (SIM) reached low ng/L levels in real samples and measured concentrations were comparable with those of SRM.
authors.affiliation: Institute of Environmental Health, College of Public Health, National Taiwan University, Taipei 10055, Taiwan.
authors.forename: Guang-Wen
authors.initials: GW
authors.lastname: Lien
authors.forename: Chia-Yang
authors.initials: CY
authors.lastname: Chen
authors.forename: Gen-Shuh
authors.initials: GS
authors.lastname: Wang
mesh_terms: D000704:Analysis of Variance; D001274:Atmospheric Pressure; D002853:Chromatography, Liquid / Q000379:methods*; D003619:Dansyl Compounds / Q000737:chemistry; D004867:Equipment Design; D004967:Estrogens / Q000032:analysis*; D005464:Fluorobenzenes / Q000737:chemistry; D005618:Fresh Water / Q000737:chemistry*; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000379:methods*; D014874:Water Pollutants, Chemical / Q000737:chemistry; D005466:Fluorocarbons
chemical_list: D003619:Dansyl Compounds; D004967:Estrogens; D005464:Fluorobenzenes; D014874:Water Pollutants, Chemical; C025063:pentafluorobenzyl bromide; D005466:Fluorocarbons; C029038:dansyl chloride