A sensitive GC–MS/MS method for the quantification of benzo[a]pyrene tetrol in urine

• Published in: Analytical and bioanalytical chemistry Vol. 416; no. 12; pp. 2913 - 2928
• Main Authors: Pilz, Fabian, Gärtner, Antonia, Pluym, Nikola, Scherer, Gerhard, Scherer, Max
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01.05.2024; Springer; Springer Nature B.V
• Subjects: Alcohols; Analysis; Analytical Chemistry; Benzo(a)pyrene; Benzo(a)pyrene-diol epoxide; Benzopyrene; Biochemistry; Biomarkers; Carcinogens; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Cigarette smoking; Cigarettes; combustion; Creatinine; Detoxification; Food Science; Gas chromatography; Hydrolysis; Identification and classification; Laboratory Medicine; Mass spectrometry; Metabolic activation; Metabolic rate; Metabolism; Monitoring/Environmental Analysis; nicotine; Occupational exposure; Organic matter; Oxidation; Polycyclic aromatic hydrocarbons; Pyrene; Research Paper; Smoking; Tobacco; Urine; Germany; GC–MS/MS; Urine; Human biomonitoring; Benzo[a]pyrene; Polycyclic aromatic hydrocarbons; Potentially reduced-risk products
• ISSN: 1618-2642; 1618-2650
• DOI: 10.1007/s00216-024-05233-9

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants formed during the incomplete combustion of organic matter such as tobacco. Among these, benzo[a]pyrene (BaP) has been classified as a known carcinogen to humans. It unfolds its effect through metabolic activation to BaP-(7 R ,8 S )-diol-(9 S ,10 R )-epoxide (BPDE), the ultimate carcinogen of BaP. In this article, we describe a simple and highly sensitive GC–NICI–MS/MS method for the quantification of urinary BaP-(7 R ,8 S ,9 R ,10 S )-tetrol (( +)-BPT I-1), the hydrolysis product of BPDE. The method was validated and showed excellent results in terms of accuracy, precision, and sensitivity (lower limit of quantification (LLOQ): 50 pg/L). In urine samples derived from users of tobacco/nicotine products and non-users, only consumption of combustible cigarettes was associated with a significant increase in BPT I-1 concentrations (0.023 ± 0.016 nmol/mol creatinine, p  < 0.001). Levels of users of potentially reduced-risk products as well as non-users were all below the LLOQ. In addition, the urine levels of six occupationally exposed workers were analyzed and showed the highest overall concentrations of BPT I-1 (844.2 ± 336.7 pg/L). Moreover, comparison with concentrations of 3-hydroxybenzo[ a ]pyrene (3-OH-BaP), the major detoxification product of BaP oxidation, revealed higher levels of 3-OH-BaP than BPT I-1 in almost all study subjects. Despite the lower levels, BPT I-1 can provide more relevant information on an individual’s cancers susceptibility since BPDE is generated by the metabolic activation of BaP. In conclusion, BPT I-1 is a suitable biomarker to distinguish not only cigarette smokers from non-smokers but also from users of potentially reduced-risk products. Graphical Abstract