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Hyphenation of a carbon analyzer to photo-ionization mass spectrometry to unravel the organic composition of particulate matter on a molecular level

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Abstract

The carbonaceous fraction of airborne particulate matter (PM) is of increasing interest due to the adverse health effects they are linked to. Its analytical ascertainment on a molecular level is still challenging. Hence, analysis of carbonaceous fractions is often carried out by determining bulk parameters such as the overall content of organic compounds (OC) and elemental carbon (EC) as well as the total carbon content, TC (sum of OC and EC), however, no information about the individual substances or substance classes, of which the single fractions consist can be obtained. In this work, a carbon analyzer and a photo-ionization time-of-flight mass spectrometer (PI-TOF-MS) were hyphenated to investigate individual compounds especially from the OC fractions. The carbon analyzer enables the stepwise heating of particle samples and provides the bulk parameters. With the PI-TOF-MS, it is possible to detect the organic compounds released during the single-temperature steps due to soft ionization and fast detection of the molecular ions. The hyphenation was designed, built up, characterized by standard substances, and applied to several kinds of samples, such as ambient aerosol, gasoline, and diesel emission as well as wood combustion emission samples. The ambient filter sample showed a strong impact of wood combustion markers. This was revealed by comparison to the product pattern of the similar analysis of pure cellulose and lignin and the wood combustion PM. At higher temperatures (450 °C), a shift to smaller molecules occurred due to the thermal decomposition of larger structures of oligomeric or polymeric nature comparable to lignocelluloses and similar oxygenated humic-like substances. Finally, particulate matter from gasoline and diesel containing 10% biodiesel vehicle exhaust has been analyzed. Gasoline-derived PM exhibited large polycyclic aromatic hydrocarbons, whereas diesel PM showed a much higher total organic content. The detected pattern revealed a strong influence of the biodiesel content on the nature of the particulate organic material.

Two-dimensional REMPI/TOF-MS spectrum of a PM loaded filter from car emissions using diesel (10% biodiesel) as fuel

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Acknowledgments

This work was financed by the Deutsche Forschungsgemeinschaft (DFG, code number ZI764_1-2). The authors thank Kochy Fung for his ongoing help and ideas for the coupling. The ambient and wood combustion samples were provided by the Helmholtz Zentrum München (Jürgen Orasche, Gülcin Abbaszade and Jürgen Schnelle-Kreis). Diesel and gasoline emission samples were received from the European Commission-Joint Research Centre (JRC) in Ispra, Italy (Kevin Douglas). Special thanks go to Simone Krüger for assistance with the instrument and measurements.

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Authors and Affiliations

  1. JMSC—Joint Mass Spectrometry Centre (UR), University of Rostock, Chair of Analytical Chemistry, Dr.-Lorenz Weg 1, 18059, Rostock, Germany

    Jana Grabowsky, Thorsten Streibel, Martin Sklorz & Ralf Zimmermann

  2. JMSC—Joint Mass Spectrometry Centre (HMGU), Helmholtz Zentrum München—German Research Center for Environmental Health (GmbH), Institute of Ecological Chemistry, Cooperation Group for Analysis of Complex Molecular Systems, Postfach 1129, 85758, Neuherberg, Germany

    Ralf Zimmermann

  3. Division of Atmospheric Sciences, DRI Desert Research Institute, 2215 Raggio Parkway, Reno, NV, 89512-1095, USA

    Judith C. Chow & John G. Watson

  4. JRC European Commission-Joint Research Centre, Institute for Energy, Sustainable Transport Unit, T.P. 230, Via Fermi, 2749, 21027, Ispra, VA, Italy

    Athanasios Mamakos

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  1. Jana Grabowsky
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Correspondence to Thorsten Streibel.

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Ralf Zimmermann currently is also Affiliate Research Professor at the DRI.

Published in the special issue Aerosol Analysis with guest editor Ralf Zimmermann.

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Grabowsky, J., Streibel, T., Sklorz, M. et al. Hyphenation of a carbon analyzer to photo-ionization mass spectrometry to unravel the organic composition of particulate matter on a molecular level. Anal Bioanal Chem 401, 3153–3164 (2011). https://doi.org/10.1007/s00216-011-5425-1

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  • DOI: https://doi.org/10.1007/s00216-011-5425-1

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