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FTIR analysis of surface functionalities on particulate matter produced by off-road diesel engines operating on diesel and biofuel

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Abstract

Fourier transform infrared spectroscopy is applied as a powerful analytic technique for the evaluation of the chemical composition of combustion aerosols emitted by off-road engines fuelled by diesel and biofuels. Particles produced by burning diesel, heated rapeseed oil (RO), RO with ethylhexylnitrate, and heated palm oil were sampled from exhausts of representative in-use diesel engines. Multicomponent composition of diesel and biofuel particles reveal the chemistry related to a variety of functional groups containing carbon, hydrogen, oxygen, sulfur, and nitrogen. The most intensive functionalities of diesel particles are saturated C–C–H and unsaturated C=C–H aliphatic groups in alkanes and alkenes, aromatic C=C and C=C–H groups in polyaromatics, as well as sulfates and nitrated ions. The distinguished features of biofuel particles were carbonyl C=O groups in carboxylic acids, ketones, aldehydes, esters, and lactones. NO2, C–N and -NH groups in nitrocompounds and amines are found to dominate biofuel particles. Group identification is confirmed by complementary measurements of organic carbon (OC), elemental carbon, and water-soluble ion species. The relationship between infrared bands of polar oxygenated and non-polar aliphatic functionalities indicates the higher extent of the surface oxidation of biofuel particles. Findings provide functional markers of organic surface structure of off-road diesel emission, allowing for a better evaluation of relation between engine, fuel, operation condition, and particle composition, thus improving the quantification of environmental impacts of alternative energy source emissions.

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Acknowledgment

Financial support by RFBR 12-05-00395_а and RFBR-NSC 12-05-92002 projects and Czech Science Foundation project 13-01438S is acknowledged. Authors thank Dr. Guenter Engling (Tsing Hua University) for manuscript corrections.

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Authors and Affiliations

  1. Skobeltzyn Institute of Nuclear Physics, Lomonosov Moscow State University, 119991, Moscow, Russia

    Olga B. Popovicheva & Elena D. Kireeva

  2. Chemical Department, Lomonosov Moscow State University, 119234, Moscow, Russia

    Natalia K. Shonija

  3. Department of Vehicles and Engines, Technical University of Liberec, 46117, Liberec, Czech Republic

    Michal Vojtisek-Lom

  4. Faculty of Mechanical Engineering, Czech Technical University of Prague, 16607, Prague, Czech Republic

    Michal Vojtisek-Lom

  5. Laboratory of Aerosol Chemistry and Physics, Institute of Chemical Process Fundamentals AS CR, 16502, Prague, Czech Republic

    Jaroslav Schwarz

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  1. Olga B. Popovicheva
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  2. Elena D. Kireeva
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  3. Natalia K. Shonija
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  4. Michal Vojtisek-Lom
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Correspondence to Olga B. Popovicheva.

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Popovicheva, O.B., Kireeva, E.D., Shonija, N.K. et al. FTIR analysis of surface functionalities on particulate matter produced by off-road diesel engines operating on diesel and biofuel. Environ Sci Pollut Res 22, 4534–4544 (2015). https://doi.org/10.1007/s11356-014-3688-8

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  • DOI: https://doi.org/10.1007/s11356-014-3688-8

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