Selective detection of monohydroxy metabolites of polycyclic aromatic hydrocarbons in urine using liquid chromatography/triple quadrupole tandem mass spectrometry.
Polycyclic aromatic hydrocarbons (PAHs) are ubiquitously present in the environment and associated with a variety of adverse health effects. Monohydroxylated PAHs (OH-PAHs), metabolites of PAHs, have been employed as biomarkers for human exposure assessment of PAHs. This manuscript describes new, selective detection methods for OH-PAHs using liquid chromatography and tandem mass spectrometry (LC/MS/MS). Electrospray ionization was operated in the negative ion mode to detect the deprotonated PAH metabolites ([M-H](-)). Hydroxylated metabolites of naphthalene, fluorene, phenanthrene, fluoranthene, pyrene, benzo[c]phenanthrene, chrysene, benzo[a]anthracene, and benzo[a]pyrene were selected for the method development. Based on the collision-induced dissociation MS/MS spectra of the selected OH-PAHs, a characteristic ion fragmentation, loss of 28 Da from the [M--H](-) ion, was identified for all of these OH-PAHs. This characteristic fragmentation was exploited for selective screening for OH-PAHs in human urine by incorporating a constant neutral loss (CNL) scan with data-dependent scanning, using a triple quadruple mass spectrometer. Selected reaction monitoring (SRM) was also used to tentatively identify isomers of the target OH-PAHs in human urine. The excellent linearity (3-4 orders of magnitude) and signal-to-noise performance provided by the SRM method allowed development of a sensitive LC/MS/MS method for measuring OH-PAHs in urine samples. The limits of detection of the SRM method ranged from approximately 0.1-5 pg on column for a suite of OH-PAHs tested in the study. The LC-SRM method was applied, following enzymatic deconjugation and solid-phase extraction of the urine, to preliminarily determine the OH-PAH concentrations in urine specimens from six Chinese non-occupationally exposed workers and seven Chinese coke oven workers.
Xu
Xu
X
Environmental Biomarker Shared Resource, The Cancer Institute of New Jersey and Environmental and Occupational Health Science Institute, University of Medicine and Dentistry of New Jersey (UMDNJ), Piscataway, NJ 08854, USA.
Zhang
Junfeng
J
Zhang
Lin
L
Liu
Weili
W
Weisel
Clifford P
CP
D002853:Chromatography, Liquid / Q000379:methods*; D006801:Humans; D008832:Microchemistry / Q000379:methods*; D016273:Occupational Exposure / Q000032:analysis; D011084:Polycyclic Aromatic Hydrocarbons / Q000652:urine*; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D016482:Urinalysis / Q000379:methods*
D011084:Polycyclic Aromatic Hydrocarbons