Determination of Sex Hormone Residues in Shrimp by EMR Solid Phase Extraction-Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry

A method for the determination of 15 sex hormones in shrimp meat by EMR solid phase extraction combined with ultra performance liquid chromatography-tandem mass spectrometry was established. The samples was extracted with 0.1 mol/L ethylenediaminetetraacetic acid disodium solution and acetonitrile solution, purified by Captiva EMR SPE cartridge, separated by CAPCELLPAK C₁₈ BB-H (3 µm, 2.1 mm×150 mm) column, and scanned by positive and negative ions of electrospray ion source. Ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with multiple reaction monitoring mode was used for detection, and blank matrix matching external standard method was used for quantification. The positive ion mobile phase was methanol and 0.1% formic acid, and androgen and progesterone were detected. The negative ion mobile phase was acetonitrile and 0.01% ammonia aqueous solution to detect estrogen. The results showed that the 15 kinds of sex hormone residues in shrimp meat samples purified by EMR solid phase extraction had a good linear relationship in the concentration range of 1~50 μg/kg, and the correlation coefficients (r) were all greater than 0.99. The detection limits of the method were 0.0015~0.436 μg/kg, and the quantitative limits were 0.0051~1.453 μg/kg. The average recoveries were 85.31%~119.84%, and the relative standard deviations were 2.11%~9.86% (n=6). The method was rapid, simple, reproducible and sensitive, which was suitable for the detection of 15 kinds of sex hormone residues in shrimp meat.