Extraction of alcohols from gasoline using solid phase microextraction (SPME)

It is common practice to add oxygenates, such as ethers or alcohols, to gasoline in areas suffering from ozone or smog problems in order to reduce pollution. The most commonly used oxygenates are ethanol (EtOH) and methyl tert-butyl ether (MTBE). However, MTBE is now forbidden by the environmental protection agency (EPA) because of the possibility of ground water contamination. The current trend is to use EtOH, therefore this work focuses on the analysis and quantification of EtOH in gasoline by solid phase microextraction (SPME). The major problem in quantifying EtOH in gasoline is the coelution of hydrocarbons with EtOH. There have been several approaches to solve this problem; among the chromatographic ones, three major types have been proposed: (1) the first one uses a detector selective for oxygen containing compounds; (2) the second one uses two or more columns; (3) and the third one uses an extraction step prior to GC analysis. In this work an extraction step with water is used prior to a solid phase microextraction (SPME) sample preparation coupled to a gas chromatographic (GC) analysis.

Solid phase microextraction is a recent technique, invented by Pawliszyn in 1989, and available commercially since 1994. A fiber is used to extract small amounts (ppm, ppb, ppt) of analytes from a solution, usually water. The fiber is beneficial in concentrating analytes. Most work using SPME has been done with hydrophobic (non polar) analytes, extracted using a polydimethylsiloxane (PDMS; non polar) coating on a fused silica fiber. Since very little work has been done with polar analytes, the novel approach of this work is the extraction of EtOH.

Since EtOH is the analyte of interest, a polar fiber, carboxen/polydimethyl siloxane (Car/PDMS) is used. Two methods are used for quantification of EtOH in gasoline: the method of a standard calibration curve, and the method of standard addition. They are both successful in quantifying the amount of EtOH in gasoline. The relative errors, with the method of standard addition, vary from 5.3% to 14%, while the ones with the method of calibration curve vary from 1.6% to 7.2%. Moreover, some extraction time studies for both direct and headspace sampling are performed. Direct sampling shows the presence of an equilibrium condition for the carboxen/PDMS fiber, for which no extraction theory is available. Conversely, headspace sampling shows no equilibrium state; after a sampling time of one hour, the amount of EtOH extracted decreases with sampling time. This is probably due to displacement of EtOH by other compounds in the fiber.