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J Sep Sci. 2016 Jul;39(13):2537-43. doi: 10.1002/jssc.201600307. Epub 2016 Jun 7.

Quantification of trace fatty acid methyl esters in diesel fuel by using multidimensional gas chromatography with electron and chemical ionization mass spectrometry.

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Defence Science and Technology Group, Fishermans Bend, Victoria, Australia.
Australian Centre for Research on Separation Science, School of Chemistry, Monash University, Clayton, Victoria, Australia.
School of Aerospace, Mechanical and Manufacturing Engineering, RMIT University, Melbourne, Victoria, Australia.


Measurement of contamination of marine and naval diesel fuels (arising from product mixing or adulteration) with biodiesel or fatty acid methyl esters can be problematic, especially at very low levels. A suitable solution for this task for trace amounts of individual fatty acid methyl esters with resolution and quantification can be achieved by using a multidimensional gas chromatographic approach with electron and chemical ionization mass spectrometric detection. A unique column set comprising a 100 m methyl-siloxane nonpolar first dimension column and high-temperature ionic liquid column in the second dimension enabled identification of individual fatty acid methyl esters at below the lowest concentrations required to be reported in a diesel fuel matrix. Detection limits for individual fatty acid methyl esters compounds ranged from 0.5 to 5.0 mg/L, with excellent linearity up to 5000 mg/L and repeatability of the method from 1.3 to 3.2%. The method was applied to the analysis of diesel fuel samples with suspected biodiesel contamination. Contamination at 568 mg/L was calculated for an unknown sample and interpretation of the results permitted the determination of a likely source of the contamination.


Biodiesel; Chemical Ionization; Fatty acid methyl esters; Fuel contamination; Multidimensional chromatography


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