Sensitive determination of trace urinary 3-hydroxybenzo[a]pyrene using ionic liquids-based dispersive liquid-liquid microextraction followed by chemical derivatization and high performance liquid chromatography-high resolution tandem mass spectrometry.
3-Hydroxybenzo[a]pyrene (3-OHBaP) is widely used as a biomarker for assessing carcinogenic benzo[a]pyrene exposure risks. However, monitoring urinary 3-OHBaP suffers from an insufficient sensitivity due to the pg/mL level in urine excretion. In this study, a sensitive method for determination trace urinary 3-OHBaP was developed, involving enzymatic hydrolysis of the glucuronide and sulfate conjugates, ionic liquids dispersive liquid-liquid microextraction (IL-DLLME) enrichment, derivatization with dansyl chloride and HPLC-HRMS/MS analysis in the positive ion mode. Using IL-DLLME makes the enrichment of trace 3-OHBaP very simple, time-saving, efficiency and environmentally-friendly. To enhanced HPLC-HRMS/MS response, an MS-friendly dansyl group was introduced to increase the ionization and fragmentation efficiency. The optimal IL-DLLME extraction parameters and derivatization reaction conditions were investigated. Good linearity was obtained over a concentration range of 0.6-50.0pg/mL with correlation coefficients (r(2)) of 0.9918. The limit of detection (LOD) and limit of quantification (LOQ) values were 0.2pg/mL and 0.58pg/mL, respectively. The recoveries were 92.0±4.2% with the intra-day and inter-day RSD values ranged from 2.2% to 3.8% and from 3.3% to 6.8%, respectively. The proposed IL-DLLME-Dansylation-HPLC-HRMS/MS method was successfully applied to determine urinary 3-OHBaP of non-occupational exposed smokers and nonsmokers.
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, PR China.
Huan
H
Hu
Key Laboratory of Cigarette Smoke Research of China National Tobacco Corporation, Shanghai 200082, PR China.
Baizhan
B
Liu
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, PR China.
Jun
J
Yang
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, PR China.
Zuomin
Z
Lin
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, PR China. Electronic address: wgan@ustc.edu.cn.
Wuer
W
Gan
D001580:Benzopyrenes / Q000032:analysis*; D002274:Carcinogens, Environmental / Q000032:analysis / Q000493:pharmacokinetics; D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D004781:Environmental Exposure / Q000032:analysis; D004785:Environmental Pollutants / Q000652:urine*; D006801:Humans; D052578:Ionic Liquids / Q000737:chemistry; D057230:Limit of Detection; D059627:Liquid Phase Microextraction / Q000379:methods*; D011084:Polycyclic Aromatic Hydrocarbons / Q000652:urine; D053719:Tandem Mass Spectrometry / Q000379:methods*
D001580:Benzopyrenes; D002274:Carcinogens, Environmental; D004785:Environmental Pollutants; D052578:Ionic Liquids; D011084:Polycyclic Aromatic Hydrocarbons; C021338:3-hydroxybenzo(a)pyrene
3-Hydroxybenzo[a]pyrene; Chemical derivatization; HPLC-HRMS/MS; Human urine; Ionic liquid dispersive liquid–liquid microextraction