A validated approach for analysis of heterocyclic aromatic compounds in sediment samples

Abstract

The scientific literature is replete with analytical methods for the analysis of homocyclic aromatic compounds especially polycyclic aromatic hydrocarbons and their alkylated analogs. However, there is a paucity of methods for the analysis of nitrogen-, sulfur- and oxygen-containing polycyclic aromatic compounds (PACs). The lack of commercially available analytical standards, the presence of many structural derivatives and isomers and lack of certified reference materials all contribute to the inherent challenges in measuring these compounds. Gas chromatography coupled with a tandem mass spectrometer was used to develop two multiple reaction monitoring methods to detect and quantify fifty-three non-halogenated and halogenated hetero-polycyclic aromatic compounds (HPACs). Because of their greater polarity, strongly non-polar solvents typically employed to extract homocyclic PACs from sediment samples did not yield acceptable recoveries of our target analytes. By adding ethyl acetate to dichloromethane (50:50), recoveries of our target analytes using accelerated solvent extraction increased markedly. The performance characteristics of the validated method including accuracy [> than 67% for 46 (out of 53) analytes], inter- and intra-day precision [<30% for all analytes, (expressed as relative standard deviation)], limits of detection (0.1 to 2.3 ng/g) and quantitation (1.5 to 7.6 ng/g) imply that the method is fit for its intended purpose. A sediment sample from a known contaminated site in Canada was analyzed for both homo- and hetero-PACs. Measured concentrations of Σ₂₇HPAC (7.3 μg/g, dry weight) were significantly smaller (p<0.05) than Σ₁₆PAHs (80.9 μg/g, dry weight) and Σ₃₀Alkylated-PAHs (14.2 μg/g, dry weight). These results suggest that the developed method is an effective and efficient approach for the targeted analysis of HPACs and their halogenated derivatives in sediment samples.

Keywords: Gas chromatography tandem mass spectrometry; Heterocyclic aromatic compounds; Polycyclic aromatic compounds; Sediments; Targeted analysis.