Avoiding Hydrolysis of Fuel Ether Oxygenates during Static Headspace Analysis

Abstract

The determination of fuel ether oxygenates in groundwater was found to be problematic when samples are preserved at pH < 2 and then analyzed using heated headspace sampling. Acid catalyzed the hydrolysis of tert-amyl methyl ether, ethyl tert-butyl ether, and methyl tert-butyl ether during headspace sampling when aqueous samples were heated at 80 degrees C, a typical temperature used for heated headspace sampling. Hydrochloric acid at pH 2 did not cause hydrolysis of oxygenate ethers in samples stored for 28 d at 4 degrees C. When trisodium phosphate was used to preserve the sample or to adjust the pH of samples preserved with acid before headspace sampling, the recovery of spiked ethers was excellent. The heated headspace method was also applicable for the determination of other fuel oxygenates including ethanol, tert-butyl alcohol (TBA), tert-amyl alcohol (TAA), isopropyl alcohol (IPA), acetone, and monoaromatic compounds found in gasoline including benzene, toluene, ethylbenzene, xylenes, and trimethylbenzenes. The method detection limits range from 0.1 to 0.2 microg/L for the ethers and aromatics. For alcohols and acetone, the method detection limits were 0.8 microg/L for TBA, 18 microg/L for ethanol, 1.2 microg/L for TAA, 5.5 microg/L for IPA, and 3.3 microg/L for acetone. The heated headspace method yielded accurate results for ether oxygenates in samples containing a wide range of gasoline concentrations (2500-100000 microg/L).