Analytical and Bioanalytical Chemistry

, Volume 406, Issue 13, pp 3119–3129

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

  • Zheng Li
  • Lovisa C. Romanoff
  • Debra A. Trinidad
  • Erin N. Pittman
  • Donald Hilton
  • Kendra Hubbard
  • Hasan Carmichael
  • Jonathan Parker
  • Antonia M. Calafat
  • Andreas Sjödin
Research Paper

DOI: 10.1007/s00216-014-7676-0

Cite this article as:
Li, Z., Romanoff, L.C., Trinidad, D.A. et al. Anal Bioanal Chem (2014) 406: 3119. doi:10.1007/s00216-014-7676-0

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.

Figure

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).

Keywords

Polycyclic aromatic hydrocarbon PAH Methylnaphthalene Human exposure Biomonitoring Biomarker 

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®

Supplementary material

216_2014_7676_MOESM1_ESM.pdf (1.6 mb)
ESM 1(PDF 1.55 kb)

Copyright information

© Springer-Verlag Berlin Heidelberg (outside the USA) 2014

Authors and Affiliations

  • Zheng Li
    • 1
  • Lovisa C. Romanoff
    • 2
  • Debra A. Trinidad
    • 1
  • Erin N. Pittman
    • 1
  • Donald Hilton
    • 1
  • Kendra Hubbard
    • 1
  • Hasan Carmichael
    • 1
  • Jonathan Parker
    • 1
  • Antonia M. Calafat
    • 1
  • Andreas Sjödin
    • 1
  1. 1.Centers for Disease Control and Prevention, National Center for Environmental Health, Division of Laboratory SciencesAtlantaUSA
  2. 2.Centers for Disease Control and Prevention, National Center for HIV/AIDS, Viral Hepatitis, STD, and TB Prevention, Division of STD PreventionAtlantaUSA