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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union
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Volume 11, issue 5 | Copyright
Atmos. Meas. Tech., 11, 3047-3058, 2018
https://doi.org/10.5194/amt-11-3047-2018
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 29 May 2018

Research article | 29 May 2018

Mapping and quantifying isomer sets of hydrocarbons (≥ C12) in diesel exhaust, lubricating oil and diesel fuel samples using GC × GC-ToF-MS

Mohammed S. Alam1, Soheil Zeraati-Rezaei2, Zhirong Liang3, Christopher Stark1, Hongming Xu2, A. Rob MacKenzie1,a, and Roy M. Harrison1,b Mohammed S. Alam et al.
  • 1Division of Environmental Health and Risk Management, School of Geography, Earth and Environmental Sciences, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK
  • 2Department of Mechanical Engineering, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK
  • 3School of Energy and Power Engineering, Beihang University, Beijing, 100191 China
  • aalso at: Birmingham Institute of Forest Research, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK
  • balso at: Department of Environmental Sciences/Center of Excellence in Environmental Studies, King Abdulaziz University, P.O. Box 80203, Jeddah, 21589, Saudi Arabia

Abstract. Airborne particles and vapours, like many other environmental samples including water, soils and sediments, contain complex mixtures of hydrocarbons, often deriving from crude oil either before or after fractionation into fuels, lubricants and feedstocks. Comprehensive 2D gas chromatography time-of-flight mass spectrometry (GC×GC-ToF-MS), offers a very powerful technique that separates and identifies many compounds in complicated hydrocarbon mixtures. However, quantification and identification of individual constituents at high ionization energies would require hundreds of expensive (when available) standards for calibration. Although the precise chemical structure of hydrocarbons does matter for their environmental impact and fate, strong similarities can be expected for compounds having very similar chemical structures and carbon numbers. There is, therefore, a clear benefit in an analytical technique which is specific enough to separate different classes of compounds and to distinguish homologous series while avoiding the need to handle each isomer individually. Varying EI (electron impact) ionization mass spectrometry significantly enhances the identification of individual isomers and 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 exhaust emissions. By using this analysis we report mass closures of ca. 90 and 75% for diesel fuel and lubricating oil, and identify 85 and 75% of the total ion current for gas- and particulate-phase diesel exhaust emissions.

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Diesel fuel, lubricating oil and diesel exhaust emissions all contain a very complex mixture of chemical compounds with diverse molecular structures. The GC × GC-ToF-MS analytical method is a very powerful way of separating and identifying those compounds. This paper describes the allocation of compounds into groups with similar molecular structures and chemical properties, which facilitates the intercomparison of very complex mixtures such as are found in diesel fuel, oil and emissions.
Diesel fuel, lubricating oil and diesel exhaust emissions all contain a very complex mixture of...
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