Development of a method to profile 2- to 4-ring polycyclic aromatic hydrocarbons in saliva samples from smokers and non-smokers by headspace-solid-phase microextraction-gas chromatography-triple quadrupole tandem mass spectrometry

Abstract

This study reports the development of a method based on headspace (HS)-solid-phase microextraction (SPME)-gas chromatography (GC)-triple quadrupole tandem mass spectrometry (MS/MS) for the quantification of 2- to 4-ring polycyclic aromatic hydrocarbons (PAHs) in saliva samples. Eight unmetabolized compounds (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene) were quantified using six deuterated PAHs as surrogate internal standards. The absence of matrix effect allowed saliva samples to be quantified by external calibration method. The optimized method resulted easy, with minimal sample pre-treatment (homogenization of the sample), and it achieved the highest sensitivity up to date: limits of quantification (LOQ) were in the 0.8–26.4 ng L-1 range, with a significant improvement in comparison with the few existing methods. Intra- and inter-run precisions provided CV values <18.1%, and accuracies within 20% of the spiked concentration. The application of the method to the analysis of fresh saliva samples collected by spitting from smokers (n = 10) and non-smokers (n = 10) showed that PAHs were quantifiable in all samples and that smokers had higher levels of all compounds than non-smokers. These results show that the method is suitable for quantifying low-boiling PAHs in saliva samples from individuals exposed at different PAH levels.