Supported-liquid phase extraction in combination with isotope-dilution gas chromatography triple quadrupole tandem mass spectrometry for high-throughput quantitative analysis of polycyclic aromatic hydrocarbon metabolites in urine

Environ Pollut. 2019 May:248:304-311. doi: 10.1016/j.envpol.2019.01.125. Epub 2019 Jan 31.

Abstract

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental contaminants with a number of them being carcinogenic. One of the approaches to assess human exposure to PAHs is to measure their urinary metabolites, monohydroxyl polycyclic aromatic hydrocarbons (OH-PAHs), with a method allowing for high throughput and short turn-around time. We developed a method to quantify nine urinary OH-PAHs by using supported liquid phase extraction (SLE) and isotope dilution gas chromatography tandem mass spectrometry (GC-MS/MS). SLE demonstrated advantages over the traditionally used liquid-liquid extraction techniques. The target analytes with spiked deuterated and 13C-labeled internal standards were extracted from urine by SLE after enzymatic cleavage of the glucuronide and sulfate conjugates. The extracted analytes were then derivatized with N-Methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA), and analyzed by GC-MS/MS. Six solvent mixtures were evaluated as the SLE extraction solvent, and pentane:chloroform (7:3, v/v) was selected due to its best overall analytical performance. Method detection limits for the 9 analytes ranged from 2.3 to 13.8 pg/mL. Precision and accuracy were satisfactory. SLE and internal isotope labeled standard combination reduced matrix effect effectively. This new method using SLE sample preparation techniques coupled with GC-MS/MS proves applicable to urinary measurements for PAH exposure studies for general population.

Keywords: Biomonitoring; Gas chromatography tandem mass spectrometry; Monohydroxylated PAHs; OH-PAHs; Supported phase extraction; Urine.

MeSH terms

  • Acetamides
  • Environmental Exposure / analysis*
  • Environmental Pollutants / urine*
  • Fluoroacetates
  • Gas Chromatography-Mass Spectrometry / methods
  • Humans
  • Indicator Dilution Techniques
  • Isotopes
  • Limit of Detection
  • Liquid-Liquid Extraction / methods
  • Polycyclic Aromatic Hydrocarbons / analysis
  • Polycyclic Aromatic Hydrocarbons / chemistry
  • Polycyclic Aromatic Hydrocarbons / urine*
  • Tandem Mass Spectrometry / methods

Substances

  • Acetamides
  • Environmental Pollutants
  • Fluoroacetates
  • Isotopes
  • Polycyclic Aromatic Hydrocarbons
  • trifluoroacetamide