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Discussion papers
https://doi.org/10.5194/acp-2019-449
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-2019-449
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.

Submitted as: research article 23 May 2019

Submitted as: research article | 23 May 2019

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This discussion paper is a preprint. It is a manuscript under review for the journal Atmospheric Chemistry and Physics (ACP).

Molecular Characterization of Polar Organic Matters in Off-road Engine Emissions Using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS): New Direction to Find Biomarkers

Min Cui1,2, Cheng Li3, Yingjun Chen4,1, Fan Zhang1, Jun Li2, Bin Jiang2, Yangzhi Mo2, Jia Li5, Caiqing Yan6, Mei Zheng6, Zhiyong Xie7, Gan Zhang2, and Junyu Zheng3 Min Cui et al.
  • 1College of Environmental Science and Engineering, Tongji University, Shanghai 200092, P.R. China
  • 2State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, P.R. China
  • 3Jinan University Institute for Environmental and Climate Research, Guangzhou, 511443, P.R. China
  • 4Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention (LAP3), Department of Environmental Science and Engineering, Fudan University, Shanghai 200433, P.R. China
  • 5School of Environmental Science and Engineering, Yangzhou University, Yangzhou 225127, P.R. China
  • 6SKL-ESPC and BIC-EAST, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, P.R. China
  • 7Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Institute of Coastal Research, Geesthacht, 21502, Germany

Abstract. The molecular composition and structure of polar organic matters (POM) in particles emitted from various vessels and excavators were characterized using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS). POM was extracted by purified water and was discussed by elemental composition which was divided into three groups, namely CHO, CHON and S-containing compounds (CHONS and CHOS). The results showed that: (i) CHO (accounting for 49 % of total POM relative peak response) was the most abundant group for all tested off-road engines, followed by CHON (33 %) and CHOS (35 %) for diesel- and HFO (heavy fuel oil)-fueled off-road equipment, respectively. (ii) The abundance and structure of the CHON group in water extracts were different in terms of engine type and load. The fraction of relative peak response of CHON was highest for excavator emissions under the working mode compared to other modes (idling and moving). Furthermore, dinitrophenol and methyl dinitrophenol were the most abundant emission species for excavators with high rated speed, while nitronaphthol and methyl nitronaphthol were more important for low rated speed vessels. (iii) The composition and structure of S-containing compounds was directly influenced by fuel oil characteristics (sulfur content and aromatic ring), with much more condensed aromatic rings in S-containing compounds observed for HFO-fueled vessels, while more abundant aliphatic chains were observed in emissions from diesel equipment. Overall, higher fractions of condensed hydrocarbons and aromatic rings in POM emitted from vessels using HFO caused strong optical absorption capacity. And different structures existing in POM could provide a direction to qualitative and quantities the exact organic compounds as tracers to distinguish the emission from diesel or HFO- fueled off-road engines.

Min Cui et al.
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Status: final response (author comments only)
AC: Author comment | RC: Referee comment | SC: Short comment | EC: Editor comment
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Short summary
Refined source apportionment is urgent needed, but hardly to achieve it due to lacking of specific biomarkers. Recently, FT-ICR MS as one of the most advanced mass spectrometry was used to analysis the probable chemical structure of polar organic matters emitted from off-road engines. We found that more condensed aromatic rings in S-containing compounds observed for HFO-fueled vessels, while more abundant aliphatic chains were observed in emissions from diesel equipment.
Refined source apportionment is urgent needed, but hardly to achieve it due to lacking of...
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