Objective: To develop a method for the simultaneous determination of 28 persistent organic pollutants (POPs), polybrominated diphenyl ethers(PBDEs), and 6 emerging brominated flame retardants(eBFRs) in traditional Chinese medicine(TCM) Hirudo, and apply the established method to the determination of flame retardants residues in 9 batches of Hirudo. Methods: Each about 1.0 g powder of the Hirudo sample was extracted by ultrasonic method with 70 mL n-hexane-dichloromethane mixture(1∶1,v/v), digested by 50% sulfuric acid silica gel overnight, purified by solid-phase extraction with a composite silica gel column using n-hexane-dichloromethane mixture(1∶1,v/v) elution. BDE-118 and 13C-BDE-209 were used as internal standards and determined by GC-NCI MS. The separation was carried out on an Agilent DB-5MS capillary column (0.25 mm×15 m, 0.1 μm). The carrier gas was high-purity helium at a flow rate of 1.0 mL·min-1. The inlet temperature was set at 290 ℃, the injection mode was pulse splitless, and the injection volume was 1 μL. The column temperature was programmed to start at 90 ℃ for 0.5 min, rising to 180 ℃ at a rate of 20 ℃·min-1, rising to 275 ℃ at a rate of 5 ℃·min-1, rising to 315 ℃ at a rate of 20 ℃·min-1, and holding for 5 min. It was operated on a triple quadrupole tandem mass spectrometer. The ion source was chemical source(CI), the reaction gas was methane, the ion source temperature was 230 ℃, the interface temperature was 300 ℃, and the scanning mode was negative ion selective ion detection mode. The conditions of negative ion selective ion detection mode were optimized, the matrix interference was removed, and the qualitative accuracy and quantitative sensitivity of mass spectrometry were improved. Results: Good linear calibration curves were established for the 34 brominated flame retardants with the correlation coefficients all above 0.999 5. The recoveries of all three- level standard addition experiment were between 63.0% and 135.6%, which met the requirements of trace determination. PBDEs and eBFRs were all detected in 9 batches of Hirudo samples, with the total amounts of 1.426-4.617 μg·kg-1 and 0.541-9.837 μg·kg-1, respectively. Conclusion: The established and validated method is accurate, sensitive and reliable. It can be used for the simultaneous determination of 34 brominated flame retardants in Hirudo. Attentions should be given to the persistent organic pollutants in Chinese medicinal materials. The method can be used for the determination of flame retardant residues in the quality control of TCM. It is suggested that the relevant departments should consider the safety limits of POPs in Hirudo and other animal drugs when formulating the quality standards of Chinese medicinal materials.
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