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. Airborne particles and vapours, like many other environmental samples including water,soils and sediments, contain complex mixtures of hydrocarbons, often derivingfrom crude oil either before or after fractionation into fuels, lubricantsand feedstocks. Comprehensive 2D gas chromatography time-of-flight massspectrometry (GC  ×  GC-ToF-MS), offers a very powerful technique thatseparates and identifies many compounds in complicated hydrocarbon mixtures.However, quantification and identification of individual constituents at highionization energies would require hundreds of expensive (when available)standards for calibration. Although the precise chemical structure ofhydrocarbons does matter for their environmental impact and fate, strongsimilarities can be expected for compounds having very similar chemicalstructures and carbon numbers. There is, therefore, a clear benefit in ananalytical technique which is specific enough to separate different classesof compounds and to distinguish homologous series while avoiding the need tohandle each isomer individually. Varying EI (electron impact) ionization massspectrometry significantly enhances the identification of individual isomersand homologous compound groups, which we refer to as “isomer sets”.Advances are reported in mapping and quantifying isomer sets of hydrocarbons( ≥ C12 ) in diesel fuel, lubricating oil and diesel exhaustemissions. By using this analysis we report mass closures of ca. 90 and75 % for diesel fuel and lubricating oil, and identify 85 and 75 % ofthe total ion current for gas- and particulate-phase diesel exhaustemissions.

atmospheric measurement techniques

Mapping and quantifying isomer sets of hydrocarbons ( ≥ C&amp;lt;sub&amp;gt;12&amp;lt;/sub&amp;gt;) in diesel exhaust, lubricating oil and diesel fuel samples using GC × GC-ToF-MS