Quantification of monohydroxylated polycyclic aromatic hydrocarbons in human urine samples using solid-phase microextraction coupled with glass-capillary nanoelectrospray ionization mass spectrometry.

Analytica chimica acta

PubMedID: 28502429

Yang BC, Fang SF, Wan XJ, Luo Y, Zhou JY, Li Y, Li YJ, Wang F, Huang OP. Quantification of monohydroxylated polycyclic aromatic hydrocarbons in human urine samples using solid-phase microextraction coupled with glass-capillary nanoelectrospray ionization mass spectrometry. Anal Chim Acta. 2017;97368-74.
Polycyclic aromatic hydrocarbons (PAHs) are environmental contaminants with carcinogenic effect raising worldwide concerns. Hydroxylated PAHs (OH-PAHs) could be formed in the body as metabolites of PAHs in human urine samples and thus considered as biomarkers of PAH exposure. In this study, five OH-PAHs including 3-phenanthrol, 1-naphthol, 2-hydroxy fluorene, 1-hydroxprene and 6-hydroxy chrysene in human urine samples were selectively enriched by C18 solid-phase microextraction (SPME), then SPME fiber was connected high voltage and then was inserted into a glass-capillary to elute and ionize the analytes for mass spectrometric (MS) detection. The coupling of SPME-MS showed excellent analytical performance for detection of urinary OH-PAHs under optimal conditions, providing an easy operation for rapid detection of a single sample within minutes. By use of internal standard (i. e. , 2-hydroxy fluorene-d9), the limit of detection (LOD) and limit of quantitation (LOQ) of OH-PAHs were found to be less than 0. 05 ng L(-1) level (S/N > 3) and less than 0. 1 ng L(-1) level (S/N > 10), respectively. The dynamic ranges of five OH-PAHs were found to be a range at 0. 1-5. 0 ng L(-1) with excellent coefficient (R(2) > 0. 99). This method also showed good precisions (intra-day: 3. 4-5. 5%, inter-day: 7. 0-9. 8%, n = 5) and good accuracy (85. 3-95. 3%, n = 5). Moreover, ion suppression and matrix effect in detection of OH-PAHs in urine were also investigated. Human urine samples collected from 12 volunteers including 6 non-smokers and 6 smokers have been successfully analyzed, it was found that individual OH-PAHs in smokers were higher than in non-smokers. This study demonstrated that SPME coupled with glass-capillary nanoESI-MS is a sensitive method for rapid detection of urinary OH-PAHs for health risk assessment of PAHs exposure.