Stir bar sorptive extraction with in situ derivatization and thermal desorption-gas chromatography-mass spectrometry for determination of chlorophenols in water and body fluid samples

A new method, stir bar sorptive extraction (SBSE) with in situ derivatization and thermal desorption (TD)-gas chromatography-mass spectrometry (GC-MS), which is used for the determination of trace amounts of chlorophenols, such as 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TrCP), 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP) and pentachlorophenol (PCP), in tap water, river water and human urine samples, is described. The derivatization conditions with acetic acid anhydride and the SBSE conditions such as extraction time are investigated. Then, the stir bar is subjected to TD followed by GC-MS. The detection limits of the chlorophenols in tap water, river water and human urine samples are 1-2, 1-2, and 10-20 pg ml−1 (ppt), respectively. The calibration curves for the chlorophenols are linear and have correlation coefficients higher than 0.99. The average recoveries of the chlorophenols in all the samples are higher than 95% (R.S.D. < 10%) with correction using added surrogate standards, 2,4-dichlorophenol-d5, 2,4,6-trichlorophenol-13C6, 2,3,4,6-tetrachlorophenol-13C6 and pentachlorophenol-13C6. This simple, accurate, sensitive and selective analytical method may be applicable to the determination of trace amounts of chlorophenols in liquid samples.