Abstract
Polycyclic aromatic hydrocarbons (PAHs) and their alkylated derivatives, such as methylnaphthalenes (MeNs), are harmful pollutants ubiquitously present in the environment. Exposure to PAHs has been linked to a variety of adverse health effects and outcomes, including cancer. Alkyl PAHs have been proposed as petrogenic source indicators because of their relatively high abundance in unburned petroleum products. We report a method to quantify 11 urinary methylnaphthols (Me-OHNs), metabolites of 1- and 2-methylnaphthalenes, and 10 monohydroxy PAH metabolites (OH-PAHs), using automated liquid-liquid extraction and isotope dilution gas chromatography tandem mass spectrometry (GC-MS/MS). After spiking urine (1 mL) with 13C-labeled internal standards, the conjugated target analytes were hydrolyzed enzymatically in the presence of ascorbic acid. Then, their free species were preconcentrated into 20 % toluene in pentane, derivatized and quantified by GC-MS/MS. The 11 Me-OHNs eluted as 6 distinct chromatographic peaks, each representing 1 − 3 isomers. Method detection limits were 1.0− 41 pg/mL and the coefficients of variation in quality control materials were 4.7 − 19 %. The method was used to analyze two National Institute of Standards and Technology’s Standard Reference Materials® and samples from 30 smokers and 30 non-smokers. Geometric mean concentrations were on average 37 (Me-OHNs) and 9.0 (OH-PAHs) fold higher in smokers than in non-smokers. These findings support the usefulness of Me-OHNs as potential biomarkers of non-occupational exposure to MeNs and sources containing MeNs.
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Abbreviations
- 1-MeN:
-
1-Methylnaphthalene
- 2-MeN:
-
2-Methylnaphthalene
- 1-NAP:
-
1-Naphthol
- 2-NAP:
-
2-Naphthol
- CV:
-
Coefficient of variation
- LOD:
-
Limit of detection
- SD:
-
Standard deviation
- 1-PYR:
-
1-Hydroxypyrene
- 3-BaP:
-
3-Hydroxybenzo[a]pyrene
- BaP:
-
Benzo[a]pyrene
- CDC:
-
Centers for Disease Control and Prevention
- 13C-IS:
-
13C-labeled internal standard
- 13C-PCB105:
-
13C12-labeled 2,3,3′,4,4′-pentachlorobiphenyl
- GC-MS/MS:
-
Gas chromatography tandem mass spectrometry
- GM:
-
Geometric mean
- LLE:
-
Liquid–liquid extraction
- MeN:
-
Methylnaphthalene
- Me-OHN:
-
Methylnaphthol
- MRM:
-
Multiple reaction monitoring
- MSTFA:
-
N-methyl-N-(trimethylsilyl)-trifluoroacetamide
- NIST:
-
National Institute of Standard and Technology
- OH-PAH:
-
Monohydroxy polycyclic aromatic hydrocarbon
- PAH:
-
Polycyclic aromatic hydrocarbon
- QC:
-
Quality control materials
- SRM:
-
Standard Reference Materials®
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Acknowledgments
The authors thank Dr. Michele Schantz for kindly providing the new SRMs and the draft Certificates of Analysis. They thank Alisha Etheredge, Lei Meng, Matthew Cohen, Ramak Ostovar, James Hand, and Sandra Lester for their contributions. The coauthors of this manuscript do not have any financial conflict of interest. Use of trade names and commercial sources is for identification purposes only and does not constitute endorsement by the CDC. The content is solely the responsibility of the authors and does not necessarily represent the official position of the CDC.
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Li, Z., Romanoff, L.C., Trinidad, D.A. et al. Quantification of 21 metabolites of methylnaphthalenes and polycyclic aromatic hydrocarbons in human urine. Anal Bioanal Chem 406, 3119–3129 (2014). https://doi.org/10.1007/s00216-014-7676-0
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DOI: https://doi.org/10.1007/s00216-014-7676-0