Simultaneous analysis of 28 urinary VOC metabolites using ultra high performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (UPLC-ESI/MSMS)

Anal Chim Acta. 2012 Oct 31;750:152-60. doi: 10.1016/j.aca.2012.04.009. Epub 2012 Apr 21.


Volatile organic compounds (VOCs) are ubiquitous in the environment, originating from many different natural and anthropogenic sources, including tobacco smoke. Long-term exposure to certain VOCs may increase the risk for cancer, birth defects, and neurocognitive impairment. Therefore, VOC exposure is an area of significant public health concern. Urinary VOC metabolites are useful biomarkers for assessing VOC exposure because of non-invasiveness of sampling and longer physiological half-lives of urinary metabolites compared with VOCs in blood and breath. We developed a method using reversed-phase ultra high performance liquid chromatography (UPLC) coupled with electrospray ionization tandem mass spectrometry (ESI/MSMS) to simultaneously quantify 28 urinary VOC metabolites as biomarkers of exposure. We describe a method that monitors metabolites of acrolein, acrylamide, acrylonitrile, benzene, 1-bromopropane, 1,3-butadiene, carbon-disulfide, crotonaldehyde, cyanide, N,N-dimethylformamide, ethylbenzene, ethylene oxide, propylene oxide, styrene, tetrachloroethylene, toluene, trichloroethylene, vinyl chloride and xylene. The method is accurate (mean accuracy for spiked matrix ranged from 84 to 104%), sensitive (limit of detection ranged from 0.5 to 20 ng mL(-1)) and precise (the relative standard deviations ranged from 2.5 to 11%). We applied this method to urine samples collected from 1203 non-smokers and 347 smokers and demonstrated that smokers have significantly elevated levels of tobacco-related biomarkers compared to non-smokers. We found significant (p<0.0001) correlations between serum cotinine and most of the tobacco-related biomarkers measured. These findings confirm that this method can effectively quantify urinary VOC metabolites in a population exposed to volatile organics.

MeSH terms

  • Biomarkers / urine
  • Chromatography, High Pressure Liquid*
  • Chromatography, Reverse-Phase
  • Cotinine / blood
  • Environmental Pollutants / metabolism
  • Environmental Pollutants / urine*
  • Smoking
  • Spectrometry, Mass, Electrospray Ionization*
  • Tobacco / chemistry
  • Volatile Organic Compounds / metabolism
  • Volatile Organic Compounds / urine*


  • Biomarkers
  • Environmental Pollutants
  • Volatile Organic Compounds
  • Cotinine