Physical and chemical characterisation of PM emissions from two ships operating in European Emission Control Areas
Authors: Moldanová J. , Fridell E. , Winnes H. , Holmin-Fridell S. , Boman J. , Jedynska A. , Tishkova V. , Demirdjian B. , Joulie S. , Bladt H. , Ivleva N. P. , Niessner R. 
Published: April 2013

Abstract. Emissions of particulate matter (PM) from shipping contribute significantly to the anthropogenic burden of PM. The environmental effects of PM from shipping include negative impact on human health through increased concentrations of particles in many coastal areas and harbour cities and the climate impact. The PM emitted by ship engines consists of organic carbon (OC), elemental or black carbon (EC/BC), sulphate, inorganic compounds containing V, Ni, Ca, Zn and other metals and associated water. The chemical composition and physical properties of PM vary with type of fuel burned, type of engine and engine operation mode. While primary PM emissions of species like V, Ni and Ca are supposed to be determined by composition of fuel and lubricant oil, emissions of particulate OC, EC and sulphate are affected both by fuel quality and by operation mode of the engine. In this paper a number of parameters describing emission factors (EFs) of gases and of particulate matter from ship engines were investigated during 2 on-board measurement campaigns for 3 different engines and 3 different types of fuels. The measured EFs for PM mass were in the range 0.3 to 2.7 g/kg-fuel with lowest values for emissions from combustion of marine gas oil (MGO) and the highest for heavy fuel oil (HFO). Emission factors for particle numbers EF(PN) in the range 5 × 1015–1 × 1017 #/kg-fuel were found, the number concentration was dominated by particles in the ultrafine mode and ca. 2/3 of particles were non-volatile. The PM mass was dominated by particles in accumulation mode. Main metal elements in case of HFO exhaust PM were V, Ni, Fe, Ca and Zn, in case of MGO Ca, Zn and P. V and Ni were typical tracers of HFO while Ca, Zn and P are tracers of the lubricant oil. EC makes up 10–38% of the PM mass, there were not found large differences between HFO and MGO fuels. EC and ash elements make up 23–40% of the PM mass. Organic matter makes up 25–60% of the PM. The measured EF(OC) were 0.59 ± 0.15 g/kg-fuel for HFO and 0.22 ± 0.01 g/kg-fuel for MGO. The measured EF(SO42−) were low, ca. 100–200 mg/kg-fuel for HFO with 1% fuel sulphur content (FSC), 70–85 mg/kg-fuel for HFO with 0.5% FSC and 3–6 mg/kg-fuel for MGO. This corresponds to 0.2–0.7% and 0.01–0.02% of fuel S converted to PM sulphate for HFO and MGO, respectively. The (scanning) transmission electron microscopy (TEM and STEM) images of the collected PM have shown three different types of particles: (1) soot composed mainly of C, O, sometimes N, and with traces of Si, S, V, Ca and Ni; (2) char and char-mineral particles composed of C, O, Ca and S (sometimes Si and Al) with traces of V and Ni and sometimes P and (3) amorphous, probably organic particles containing sulphur and some vanadium. The maps of elements obtained from STEM showed heterogeneous composition of primary soot particles with respect to the trace metals and sulphur. Composition of the char-mineral particles indicates that species like CaSO4, CaO and/or CaCO3, SiO2 and/or Al2SiO5, V2O5 and Fe3O4 may be present; the last two were also confirmed by analyses of FTIR spectra of the PM samples. The TPO of PM from the ship exhaust samples showed higher soot oxidation reactivity compared to automotive diesel soot, PM from the HFO exhaust is more reactive than PM from the MGO exhaust. This higher oxidation reactivity could be explained by high content of catalytically active contaminants; in particular in the HFO exhaust PM for which the energy-dispersive X-ray spectroscopy (EDXRF) analyses showed high content of V, Ni and S. Oxidative potential measured as a rate of consumption of consumption of Dithiothreitol (DTT) was for the first time measured on PM from ship exhaust. The obtained values were between 0.01 and 0.04 nmol-DTT/min/μg-PM, quite similar to oxidative potentials of PM collected in urban and traffic sites. The data obtained during the experiments add information on emission factors for both gaseous and PM-bound compounds from ship engines using different fuels and under different engine load conditions. Observed variability of the EFs illustrates uncertainties of these emission factors as a result of measurement uncertainties, influences from trace components of fuels and lubricants and from differences between individual engines.