Thermal/optical Carbon Analysis coupled with
Photoionization Time-of-Flight Mass Spectrometry:
Fine Particulate Matter from a Marine Engine
H. Czech1 ● O. Sippula2,3 ● M. Sklorz1 ● T. Streibel1,3,4 ● R. Zimmermann1,3,4
Introduction
Method
 worldwide 90% of goods are transported by ships
ISO 8178-4 E2
Marine Engine & Fuels
average load
 four stroke
 particulate emissions (PM): several million tons per year
 one cylinder
→ mainly soot, metals, sulfates, nitrates and hazardous organics
 80 kW, 1500 rpm
 HFO (1.6 % sulfur)
one quartz filter sample
 ship-related PM is linked to cardiovascular diseases
 DF (10 ppm sulfur)
 affects radiative forcing depending on its composition
Fig. 1 ISO 8178-4 E2 engine cycle and sampling period
 95% of ships run with heavy fuel oil (HFO, ~2.7% fuel-sulfur average)
Single Photon Ionization (SPI)
 fuel-sulfur enhances PM formation through its conversion to sulfate
M+ + e-
E
2X
 performed @118nm (E = 10.49 eV)
 universal and fragment-free
 Sulfur Emission Control Areas (SECA) with 0.1% fuel-sulfur since 2015
 if ionization energy ≤ photon energy
Scope
1S
M
0
Resonance-enhanced Multiphoton Ionization (REMPI)
 performed @266nm ( E = 4.66 eV)
How does the carbonaceous particulate emission change when ships
M+ + e-
E
2X
 two-photon process with transition state
 selective for aromatic species
switch from heavy fuel oil (HFO) to low-sulfur diesel fuel (DF)?
Fig. 2 hyphenation carbon analyzer to TOF
M
1S
1
1S
0
Results and Discussion
Single Photon Ionization (SPI)
diesel fuel (DF)
Resonance-enhanced
Multiphoton Ionization
(REMPI)
 only PAH: alkylated phenanthrenes and naphthalenes
together with C0- to C2-pyrene
 absence of large polyaromatic structures
 fatty acid methyl esters (FAME) from biodiesel:
most abundant species
 naphthalic anhydride and alkanes
Thermodesorption: 25°C – 280°C
Pyrolysis: 280°C – 580°C
heavy fuel oil (HFO)
 domination of alkylated PAH, such as phenanthrenes,
chrysenes and benz[a]pyrenes, and the homologue
series of heteroaromatic dibenzothiophene
 thermal decomposition products hydrogen sulfide,
methane thiol and carbon disulfide indicate abundance
of sulfur in low-volatile fraction
Student‘s t-Test
Carbon Analysis
Fig. 3 a+b) thermodesorption-like and c+d) pyrolysis-like thermal fractions of DF (blue) and HFO (red)
Conclusion
alkyl-naphthalenes
elemental carbon
PAH alkylation
3-Ring PAH
organic carbon
DF
FAME
Fig. 4 [above] organic (OC), elemental (EC) and
total carbon content (TC) of DF- and HFO-particles
Fig. 5 [left] significantly enhanced m/z in HFO
(black), DF (white) or none (grey)
HFO
alkanes
naphthalic anhydride
≥5-Ring-PAH
dibenzothiophenes
Literature
O. Sippula et al., Environmental Science and Technology 48, 11721 (2014).
J. Grabowsky et al., Analytical and Bioanalytical Chemistry 401, 3153 (2011).
Contact: [email protected], [email protected], [email protected]
1University
of Rostock, Institute of Chemistry, Department of Analytical Chemistry & Joint Mass Spectrometry Centre, 18051 Rostock, Germany
2University
of Eastern Finland, Department of Environmental Science, Kuopio, FI-70101, Finland
3Helmholtz
Virtual Institute of Complex Molecular Systems in Environmental Health (HICE) - www.hice-vi.eu
4Helmholtz
Zentrum München, Institute of Environmental Chemistry, Cooperation Group “Complex Molecular Systems“, 85764 Neuherberg, Germany