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Quantification of 21 metabolites of methylnaphthalenes and polycyclic aromatic hydrocarbons in human urine

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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.

A gas chromatogram of a standard containing the trimethylsilyl derivatives of 11 methylnaphthols and 10 monohydroxylated PAHs (1 pg injection on column for 1- and 2-naphthol, 250 fg for the remaining analytes).

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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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Authors and Affiliations

  1. Centers for Disease Control and Prevention, National Center for Environmental Health, Division of Laboratory Sciences, 4770 Buford Highway F-53, Atlanta, GA, 30341, USA

    Zheng Li, Debra A. Trinidad, Erin N. Pittman, Donald Hilton, Kendra Hubbard, Hasan Carmichael, Jonathan Parker, Antonia M. Calafat & Andreas Sjödin

  2. Centers for Disease Control and Prevention, National Center for HIV/AIDS, Viral Hepatitis, STD, and TB Prevention, Division of STD Prevention, 4770 Buford Highway F-53, Atlanta, GA, 30341, USA

    Lovisa C. Romanoff

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  1. Zheng Li
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Correspondence to Zheng Li.

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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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