Simultaneous determination of polycyclic aromatic hydrocarbons and tobacco-specific N-nitrosamines in mainstream cigarette smoke using in-pipette-tip solid-phase extraction and on-line gel permeation chromatography-gas chromatography–tandem mass spectrome

• In-pipette-tip SPE was applied for purification of mainstream smoke (MSS) extract.
• The sample preparation process can be accomplished within a very short time.
• A method for simultaneous determination of PAHs and TSNAs in MSS was established.
• The method has the advantages of simplicity, rapidity and high-efficiency.

In this study, a silica/primary secondary amine (SiO2/PSA) was used as an in-pipette-tip solid phase extraction (SPE) sorbent for the simultaneous determination of polycyclic aromatic hydrocarbons (PAHs) and tobacco-specific N-nitrosamines (TSNAs) in mainstream cigarette smoke (MSS). We investigated several parameters including an extraction procedure of total particulate matter, type and amount of sorbent and on-line gel permeation chromatography parameters to obtain optimum conditions for a new strategy to target analytes. Under the optimized conditions, we developed a method for the simultaneous determination of PAHs and TSNAs in MSS by coupling in-pipette-tip SPE procedures to an on-line gel permeation chromatography-gas chromatography–tandem mass spectrometry (on-line GPC-GC–MS2). Our method had limits of detection for target analytes ranging from 0.01 to 0.23 ng/cig. Good linearities were obtained with coefficients of determination (R2) greater than 0.9984 for all target analytes. Good reproducibility was obtained as intra- and inter-day precisions, and the relative standard deviations were less than 11.4 and 13.3%, respectively. The recoveries were in the range of 77.1–108.6% at different concentrations for real samples. Compared to previous standard methods for the determination of PAHs and TSNAs in MSS, our method was highly effective, fast, and had low consumption of organic solvent and a high degree of automation. Finally, our method successfully analyzed PAHs and TSNAs in real samples, and no significant deviations were observed when compared to similar analysis using standard methods.