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. The molecular compositions of polar organic compounds (POCs) inparticles emitted from various vessels and excavators were characterizedusing Fourier transform ion cyclotron resonance mass spectrometry (FT-ICRMS), and possible molecular structures of POCs were proposed. POCs wereextracted with purified water and sorted by elemental composition into threegroups: CHO, CHON, and S-containing compounds (CHONS and CHOS). The resultsshow the following. (i) CHO (accounting for 49 % of total POCs in terms of peakresponse) 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 engines. (ii) The abundance andstructure of the CHON group in water extracts were different in terms ofengine type and load. The relative peak response of CHON was the highest forexcavator emissions in working mode, compared to the idling and movingmodes. Furthermore, dinitrophenol and methyl dinitrophenol were potentiallythe most abundant emission species for high-rated speed excavators, whilenitronaphthol and methyl nitronaphthol were more important for low-ratedspeed vessels. (iii) The composition and structure of the S-containingcompounds were directly influenced by fuel oil characteristics (sulfurcontent and aromatic ring), with more condensed aromatic rings in theS-containing compounds proposed in HFO-fueled vessel emissions. Moreabundant aliphatic chains were inferred in diesel equipment emissions.Overall, higher fractions of condensed hydrocarbons and aromatic rings inPOCs emitted from vessels using HFO cause strong optical absorptioncapacity. Different structures in POCs could provide a direction forqualitative and quantitative analysis of organic compounds as tracers todistinguish these emissions from diesel or HFO-fueled off-road engines.

atmospheric chemistry and physics

Molecular characterization of polar organic aerosol constituents in off-road engine emissions using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS): implications for source apportionment