Simultaneous determination of eleven estrogenic and odorous chloro- and bromo-phenolic compounds in surface water through an automated online headspace SPME followed by on-fiber derivatization coupled with GC-MS

Abstract

An effective method based on automated online headspace solid-phase microextraction (HS-SPME) followed by on-fiber derivatization coupled with gas chromatography-mass spectrometry (GC-MS) for simultaneous determination of eleven estrogenic and odorous chloro- and bromo-phenolic compounds was developed. The target chemicals included seven chlorophenols (CPs): 2-chlorophenol (2-CP), 4-chlorophenol (4-CP), 2-chloro-4-methyl phenol (2-C-4-MP), 4-chloro-2-methyl phenol (4-C-2-MP), 4-chloro-3-methyl phenol (4-C-3-MP), 2,6-dichlorophenol (2,6-DCP), and 2,4,5-trichlorophenol (2,4,5-TCP) and four bromophenols (BPs): 2-bromophenol (2-BP), 2,6-dichlorophenol (2,6-DBP), 2,4-dichlorophenol (2,4-DBP), and 2,4,6-tribromophenol (2,4,6-TBP). The extraction temperature, extraction time, derivatization time, salt concentration and pH of sample solution were optimized and determined in this study. The developed method using the optimized conditions was validated with respect to the linearity (R² > 0.991), low limit of detection (LOD, 8.8–42.9 ng L⁻¹), and excellent recoveries (69–108%) with a low relative standard deviation (RSD, 1.5–18.6%). This method provides an effective online extraction and derivatization process with good sensitivity in GC-MS, and can be applied for the efficient determination of chloro- and bromo-phenolic compounds in surface water.