RATIONALEBenzo[a]pyrene (B[a]P) is a well-known carcinogenic compound produced from incomplete combustion of organic compounds. During cigarette smoking, cigarette filters trap a portion of mainstream smoke B[a]P and accurate measurement of B[a]P levels in cigarette filter can be used to estimate human exposure level of this compound. METHODSA rapid and sensitive method to quantify B[a]P levels trapped by cigarette filter was developed. The method is based on liquid chromatography/atmospheric pressure photoionization tandem mass spectrometry (LC/APPI-MS/MS). Validation was provided in smoked cigarette filter. RESULTSThe method involved no extensive manual cleanup and concentration steps, hence is easy to use. The limit of detection was 0.064ng/mL. The recovery ranged from 82.68% to 103.27% and the relative standard deviation (RSD) was less than 7%. A regression model between mainstream cigarette smoke and trapped B[a]P by cigarette filter was established (y=2.5089x - 0.1851, R2=0.999, n=6). This model was applied to estimate mouth-level B[a]P exposure of smokers. CONCLUSIONSThe LC/APPI-MS/MS method developed in this work had an excellent throughput in estimating the mouth-level exposure under natural human smoking conditions. Mouth-level B[a]P exposure based on a study of three cigarettes (8, 10 and 13mg tar levels) showed significant positive correlations with B[a]P trapped by cigarette filter measured (y=2.5456x - 0.5056, R2=1, n=249). Copyright (c) 2014 John Wiley & Sons, Ltd.