A comprehensive, sensitive and high-throughput liquid chromatography-atmospheric pressure photoionization tandem mass spectrometry (LC-APPI-MS/MS) method has been developed for analysis of 36 halogenated flame retardants (HFRs). Under the optimized LC conditions, all of the HFRs eluted from the LC column within 14min, while maintaining good chromatographic separation for the isomers. Introduction of the pre-heated dopant to the APPI source decreased the background noise fivefold, which enhanced sensitivity. An empirical equation was proposed to describe the relation between the ion intensity and dopant flow. The excellent on-column instrument detection limits averaged 4.7pg, which was similar to the sensitivity offered by gas chromatography-high-resolution mass spectrometry (GC-HRMS). This method was used to analyze a series of fish samples. Good agreement was found between the results for PBDEs from LC-APPI-MS/MS and GC-HRMS.
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