Simultaneous determination of polycyclic aromatic hydrocarbon quinones by gas chromatography-tandem mass spectrometry, following a one-pot reductive trimethylsilyl derivatization

J Chromatogr A. 2016 Aug 12:1459:89-100. doi: 10.1016/j.chroma.2016.06.034. Epub 2016 Jun 18.

Abstract

We developed a sensitive and selective method to simultaneously analyze 37 polycyclic aromatic hydrocarbon quinones (PAHQs) with GC-MS/MS and applied the method to the analysis of standard atmospheric particulate matter samples. PAHQs were reduced with zinc granules and dithiothreitol (DTT) and the reductants were immediately converted to their silylated derivatives in a test tube. Two trimethylsilyl (TMS) groups were introduced into PAHQs through the one-pot reductive TMS derivatization. The PAHQs were derivatized with a mixed silylation reagent (BSA+TMCS+TMSI; (3:2:3)), which is one of the combinations of TMS-derivatization reagents with the highest reactivity. The derivatives produced different fragmentation between o-PAHQs and p-PAHQs. Therefore, isomers that have the same molecular weight are difficult to separate on a column were separated by the selected reaction monitoring (SRM) mode using the characteristic fragmentations, allowing separation and detection of all PAHQ derivatives in less than 30min. The instrumental detection limit (IDL) of each PAHQ was 1.2-29fg/injection and the method quantification limit (MQL) was 0.8-78μg/kg sample. For quantification, six deuterated PAHQs were used as internal standards to achieve high analytical precision. We applied the developed method to four standard atmospheric particulate matter samples. Results showed that out of 37 PAHQs, 33 compounds were identified and quantified. Moreover, from the 33 PAHQs, 14 were detected for the first time. Similar values were observed for the concentrations of PAHQs that have been quantified in previous reports. This method has the highest practicality in monitoring PAHQs in atmosphere, combustion exhaust gas, and toxicity evaluation. Thus, the method has the potential to become a standard analytical method for such applications.

Keywords: Atmospheric pollution; GC–MS/MS; Polycyclic aromatic hydrocarbon quinones; Trimethylsilyl derivatization.

MeSH terms

  • Air Pollutants / analysis*
  • Air Pollutants / chemistry
  • Air Pollutants / standards
  • Calibration
  • Gas Chromatography-Mass Spectrometry* / standards
  • Limit of Detection
  • Particulate Matter / analysis
  • Polycyclic Aromatic Hydrocarbons / chemistry*
  • Quinones / analysis*
  • Quinones / chemistry
  • Quinones / standards
  • Trimethylsilyl Compounds / chemistry*
  • Vehicle Emissions / analysis

Substances

  • Air Pollutants
  • Particulate Matter
  • Polycyclic Aromatic Hydrocarbons
  • Quinones
  • Trimethylsilyl Compounds
  • Vehicle Emissions