Aromatic hydrocarbons extracted by headspace and microextraction methods in water-soluble fractions from crude oil, fuels and lubricants

Abstract

Two extraction protocols were developed for the determination of mono- and poly-aromatic hydrocarbons in water-soluble fractions from gasoline, diesel, crude, mineral insulating, and lubricant oils. Development of the procedures was based on clean miniaturized strategies, such as headspace extraction and vortex-assisted dispersive liquid micro-extraction, together with quantification by gas chromatography-mass spectrometry. The mono-aromatic hydrocarbons were extracted using the headspace extraction method. The linear range obtained was 10-500 µg L^-1, with r² > 0.99. Based on the parameters of the analytical curves, detection and quantification limits of 2.56-3.20 and 7.76-9.71 µg L^-1 were estimated. In addition, the method showed adequate recoveries of 69.4-83.5%, with a satisfactory precision of 4.7-17.1% (n = 5). Micro-extraction was applied for the poly-aromatics and the most favorable variables were sample volume (5.00 mL) in sodium chloride medium (1%, w/v), trichloromethane as extractor solvent (75 µL), acetone as disperser (925 µL) and vortexing for 1 min. Under these conditions, analytical curves of 0.15-4.00 µg L^-1 were obtained and limits of determination and quantification were 0.03-0.15 and 0.09-0.46 µg L^-1, respectively. Recovery values of 87.6-124.5% and a maximum relative standard deviation of 18.9% (n = 5) verify satisfactory accuracy and precision. This led to the achievement of enrichment factors for poly-aromatic hydrocarbons of 41-89 times. Finally, the methods were employed in samples of water-soluble fractions for the determination of analytes. The values followed the order: gasoline > diesel > crude > lubricant > mineral insulating oil. These results indicate an increase in lighter fractions, followed by poly-aromatics in more refined products.

Keywords: Diesel; Dispersive liquid-liquid microextraction; Gasoline; Mineral insulating oil; Monoaromatics hydrocarbons; Polycyclic aromatic hydrocarbons.