Ionic liquid based dispersive liquid–liquid microextraction (IL-DLLME) combined with high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) for the determination of mercury species in liquid cosmetic samples is described. Firstly mercury (Hg2+), methylmercury (MeHg+) and ethylmercury (EtHg+) were complexed with ammonium pyrrolidinedithiocarbamate (APDC), and then the complexes were extracted into 1-hexyl-3-methylimidazolium hexafluorophosphate ([C6MIM][PF6]) using DLLME. Under the optimized conditions, the enrichment factors of 760, 115, 235 for Hg2+, MeHg+ and EtHg+ were obtained from only 5.00 mL sample solution. The detection limits of the analytes (as Hg) were 1.3 ng L−1 for Hg2+, 7.2 ng L−1 for MeHg+ and 5.4 ng L−1 for EtHg+, respectively. The relative standard deviation (n = 10) of 0.5 ng mL−1 Hg2+, MeHg+ and EtHg+ were 7.4%, 5.2% and 2.3%, respectively. Finally, the developed method was successfully applied for the speciation of mercury in four liquid cosmetic samples, Hg2+ was found as the main species in these samples, and a spike test was performed to verify the accuracy of the method.
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