Journal of Marine Engineering & Technology

ISSN: 2046-4177 (Print) 2056-8487 (Online) Journal homepage: http://www.tandfonline.com/loi/tmar20

Effects of high sulphur content in marine fuels on

particulate matter emission characteristics

Sergey Ushakov, Harald Valland, Jørgen B Nielsen & Erik Hennie

To cite this article: Sergey Ushakov, Harald Valland, Jørgen B Nielsen & Erik Hennie (2013)
Effects of high sulphur content in marine fuels on particulate matter emission characteristics,
Journal of Marine Engineering & Technology, 12:3, 30-39

To link to this article: https://doi.org/10.1080/20464177.2013.11020283

Published online: 01 Dec 2014.

Submit your article to this journal

Article views: 3385

View related articles

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=tmar20
 Effects of high sulphur content in marine fuels on particulate matter emission characteristics

Effects of high sulphur content in

marine fuels on particulate matter
emission characteristics
Sergey Ushakov, Department of Marine Technology, Norwegian University of Science and
Technology, Trondheim, Norway; MARINTEK AS, Trondheim, Norway
Harald Valland, Department of Marine Technology, Norwegian University of Science and
Technology, Trondheim, Norway
Jørgen B Nielsen, MARINTEK AS, Trondheim, Norway
Erik Hennie, MARINTEK AS, Trondheim, Norway

The effect of high sulphur level in marine fuels on diesel exhaust particulate number
distributions and mass concentrations was investigated. A strong correlation between
increase of emitted particle mass and number and increase in fuel sulphur content was
found, with the most affected particles found in the nanoparticle size range. These par-
ticulates consist of nucleated/condensed hydrocarbon and sulphur compounds, which are
potentially the most hazardous to human health. Nucleation mode particles were found
to be greatly affected by primary dilution temperature (PDT), an increase in which cause
the vapour pressures of volatile species to rise, considerably slowing down the nucleation
process. However, even at PDT=400°C this mode was not entirely eliminated, since with
­high-sulphur fuels the concentrations of nucleation-prone vapour-phase volatile compo-
nents are very high, and higher primary (and overall) dilution ratios are therefore required.
The soot fraction, which made up most of the particle mass, was only slightly affected by
sulphur content and is unaffected by PDT, although it was influenced by engine operating
parameters such as load and speed.

AUTHORS’ BIOGRAPHIES and combustion, thermofluid systems and thermodynam-

Sergey Ushakov gained his MSc from St Petersburg State Marine
Technical University, Russia, in 2008 and PhD from the Norwegian
University of Science and Technology (NTNU) in 2012. He is cur-
rently a research scientist at MARINTEK, and his main research
interests are related to the measurement and characterisation of
particulate matter emissions from marine engines and fuels.
Harald Valland is a professor of marine technology
at the Norwegian University of Science and Technology
(NTNU), where he took both his MSc and PhD degrees.
He has more than 35 years of experience in IC engines
ics as well as in the modelling and simulation of marine
machinery systems.
Jørgen Bremnes Nielsen graduated from NTNU with an
MSc in 2009 and is currently a research engineer in MARINTEK.
His field of work is related to measurements of gaseous and
PM emissions from diesel engines.
Erik Hennie is a senior engineer at MARINTEK. He is also an
MSc from NTNU and has more than 25 years experience of
combustion, alternative fuels and emission-reduction technolo-
gies in ships.

Volume 12  No 3 September 2013       Journal of Marine Engineering and Technology 30

Ushakov_JMET_Sep.indd 30 06/11/13 6:11 PM

 Effects of high sulphur content in marine fuels on particulate matter emission characteristics
INTRODUCTION
I
n the course of the past few years, diesel particulate
matter (PM) emissions have begun to attract a great deal
of attention among policymakers and aerosol scientists,
as a number of epidemiological and toxicological stud-
ies1–5 have demonstrated the existence of a strong statistical
correlation between adverse health effects and the exposure
to fine and ultrafine particles. Among the effects of long-term
exposure to diesel particulates are asthma, pulmonary and
cardiovascular diseases, cancer and elevated blood pressures
with associated complications1. Another concern regarding
PM is its impact on the Earth’s radiation balance, visibility
impairment, and atmospheric chemistry.6 Not surprisingly,
great efforts have been recently taken to characterise and
reduce diesel particulate matter emissions from both road
traffic and off-road sources.
Most particles produced by combustion process in a ­diesel
engine are normally corresponding to the size range from
3nm to 1μm in diameter, usually with a bimodal distribution
with two distinctive modes: nucleation and accumulation. The
size ranges for these modes are highly dependent on engine
technology. Particles below 30–50nm normally correspond to
nanoparticles and usually result in so-called ‘nucleation’ mode
peak, which typically contains 1–20% of the total particle mass
and up to 95% of the number of particles7,8, with the majority
of PM consisting of hydrocarbons and hydrated sulphuric acid
condensates formed during the dilution process.9,10 Some nano-
particles may have solid cores of non-volatile species such as
carbon and ash compounds, originated from lubrication oil11–13
although this is still a matter of debate.14 The second mode is
called ‘accumulation’, and it usually contains most of the parti-
cle mass, with the mode peak being in the range of 50–150nm.
It consists of agglomerated solid carbon particles, together with
associated absorbed materials such as heavy hydrocarbons,
sulphates and various ash species.15
The main aim of this paper was to describe the effect of a
high level of sulphur in fuel on PM characteristics. Previous
research investigations16,17 have shown that changing fuel
sulphur levels does not lead to any observable effects on
gaseous engine emissions, but at the same time sulphur was
found to be very important with regard to PM emissions.18,19
In order to minimise the potential adverse health effects asso-
ciated with diesel emissions from all sources, environmental
regulation authorities require the use of lower-sulphur fuels
(until the early 1990s this was not regulated). The automo-
tive industry, which has achieved significant results in diesel
emission reduction, had to shift to ultralow sulphur or even
sulphur-free fuels in order to be able to use modern diesel
particulate filters and to meet current strict environmental
standards. However, reducing fuel sulphur content to zero
will not alone eliminate the problem of particulate matter
emissions, since PM is made up of a wide variety of com-
ponents such as carbonaceous fractions, sulphates and water,
partially burned fuel and lubrication oil, etc. Lowering fuel
sulphur content thus has only limited potential in terms of
PM control.20 At the same time, the number of particles can
be lowered substantially by reducing fuel sulphur content, so
in view of the regulation of total particle number introduced
as part of the Euro 5 standard, the importance of fuel sulphur
level may increase.
31 Journal of Marine Engineering and Technology      Volume 12  No 3 September 2013
Ushakov_JMET_Sep.indd 31
Although a large number of studies deal with PM from
automotive fuels, only a few21–24 discusses particulate emis-
sions from marine fuels and engines. Most marine fuels are
typical residual oil fuels that contain up to 3.5% of sulphur
and other incombustible impurities, such as ash-forming spe-
cies, making shipping a significant PM contributor to air pol-
lution.25,26 There is lack of sufficient knowledge about the sole
effect of high-sulphur content in marine fuels on the particle
emission characteristics from marine diesel engines (MDE),
as no previous research has been done on this topic. The need
for such studies is therefore obvious, as these would enable
widely used dilution methodology to be validated for fuels
that produce very high quantities of nucleation-prone sul-
phates and HC compounds, revealing potential measurement
artifacts and thus expanding our understanding of important
aspect of dilution. Moreover, in the future, such results will
be useful when the effectiveness of International Maritime
Organization (IMO) fuel sulphur regulations27 in reducing the
mass and number of emitted PM is being evaluated.
It is not easy to isolate the individual effect of sulphur from
other fuel impurities such as ash and metal sediments21, but in
current work, in order to overcome this difficulty we artificially
doped distillate marine fuel with relatively low sulphur content
with dimethyl disulphide (DMDS) to desired levels of sulphur
content. This enabled us to reproduce, if not exactly to initiate,
the molecular structure and content of natural sulphur-bearing
compounds19, 28 in marine heavy fuel oils. Analytical grade
(99% purity) DMDS, which is essential for such experiments
is very expensive and is required in large quantities for MDE.
In order to minimise costs we therefore decided to perform
experiments on smaller high-speed heavy-duty engine for the
early stages of the project and later, after data analysis and
optimisation of the experimental set-up and test sequence, to
validate the results in full-scale MDE experiments. The authors
are aware that the findings of the current study cannot simply
be extended to all marine-type engines without additional
validation. We plan to do so, but we believe that the results
already obtained are valuable, as the effects of sulphur level in
fuel can reasonably be studied under certain high- and low-load
conditions, along with the behaviour of commercially available
dilution systems that operate under such interesting conditions.
To summarise, the core goal of this study was to study in
isolation the effects of high sulphur levels in marine fuels on
particulate mass and numbers, emitted by a diesel engine under
various operating conditions. The study also addresses the
influence of a two-stage dilution system, with emphasis on the
influence of the primary dilution temperature on PM emissions.
A further aim was to pinpoint the importance of marine fuel
sulphur as a contributor to air pollution and to encourage the
development of standards for particulate emissions from MDEs.
Experimental Methods
Test engine, fuels and operating conditions
The test engine used was a 280kW 6-cylinder turbocharged,
inter-cooled heavy-duty Scania DC1102 diesel engine that
fully complied with the EURO 2 emission tier. This is a
four-stroke high-speed direct-injection engine with a cylinder
displacement of 10.64L and a peak torque of 1750Nm. The
06/11/13 6:11 PM
 Effects of high sulphur content in marine fuels on particulate matter emission characteristics
engine was installed on a test-bed based on a dynamometer
water brake in our laboratory.
The conventional marine gas-oil (MGO) diesel fuel,
which was the baseline fuel of the study, was supplied by A/S
Norske Shell, and represents a typical low-sulphur MGO.
This fuel is almost free of asphaltenes and ash, and contains
only 0.05% S (by weight). The properties of MGO are very
similar to EURO 2 standard diesel fuel for on-road vehicles.
We used the organosulphur compound dimethyl disul-
phide (DMDS, C2H6S2) as a sulphur additive compound. It
was of 99% purity and was blended with baseline fuel in
ratios of approximately 1/42 and 1/20 (by volume), which
resulted in fuel sulphur contents of 2% and 4% (by mass)
respectively. The solubility properties of DMDS in diesel
fuel were tested in advance at blending ratios of up to 1/1 and
showed no signs of phase separation in the course of a week
of monitoring. There was therefore no need for any special
emulsifying agent. The major properties of all the test fuels
and DMDS are shown in Table 1.
Particulate characteristics were obtained at steady states in
nine operating modes (10–35min at each). The corresponding
engine parameters are shown in Table 2 and were selected
from a 13-mode steady-state ECE R49 diesel emission test
cycle for heavy-duty diesel engines6, 29, which we adopted as a
basis for the study. The full cycle was not applicable because
of engine brake limitations; and it was not possible to exceed
75% load. In each test, the engine was run for 10–15min
until all temperatures and measured NOx concentrations had
stabilised. All steady-state tests were repeated three times to
ensure reproducibility of the results.
Sampling and dilution procedures
Engine exhaust samples were extracted from the tailpipe with
the help of a sharp-edged open-ended probe installed near the
Fig 1: Schematic diagram of the experimental set-up
Volume 12  No 3 September 2013       Journal of Marine Engineering and Technology
Ushakov_JMET_Sep.indd 32
centreline of the exhaust pipe. The sampled gas was brought
to the dilution system by means of a heated sampling line.
The sampling line was 1.5m long, electrically heated and
insulated in order to maintain the volatile species in sampled
the stream above the dew-point and to reduce particle losses
caused by thermophoresis.9, 30 Nevertheless, a correction pro-
cedure, based on well-known correlations31, was employed
in order to account for various particle losses which inher-
ently occur during gas sampling. A schematic diagram of the
experimental setup is shown in Fig 1.
A two-stage dilution system32, 33 (Dekati Ltd, Finland)
comprising a primary porous tube diluter and secondary ejec-
tor diluter was utilised during this study. Main advantages
and disadvantages of the system were investigated in earlier
studies.34, 35 The process of dilution, whereby a portion of
sampled gas is mixed with particle-free dry air, simulates the
actual physical and chemical processes that occur when hot
combustion gases interact with much cooler ambient air. A
number of studies8, 15, 32, 36, 37 have demonstrated that dilution
parameters such as temperature, humidity, residence time and
dilution ratio have significant effect on particle formation,
especially in nucleation mode size range. Although dilution
issues were not the main subject of the study, we decided to
investigate the effect of primary dilution temperature (PDT)
on PM emissions. Two very different PDT settings were
therefore employed at the primary porous tube, resulting in
‘hot’ and ‘cold’ dilution respectively, while the secondary
(ejector) diluter air temperature was maintained at ambient
level throughout the study. The ‘hot’ dilution (PDT=400°C)
settings allowed to study mainly solid (non-volatile) particles,
while PM measured after the ‘cold’ dilution (PDT=30°C)
contained both solid carbonaceous PM with absorbed and/
or condensed (or nucleated) volatile and semi-volatile mate-
rial9 often denoted as soluble organic fraction. The primary
dilution ratio varied slightly within the range of 5–7 and was
32
06/11/13 6:11 PM
 Effects of high sulphur content in marine fuels on particulate matter emission characteristics

Marine gas oil Dimethyl

Properties 2% S fuel 4% S fuel
(MGO) disulphide, 99%
Sulphur content, % wt 0.05 68.1 2.0 4.0
Lower heating value, MJ/kg 42.6 21.8 42.0 41.4
Density at 20° C, kg/m3 840 1046 845.9 852.0
MGO, % wt 100 0 97.14 94.19
Dimethyl disulphide, % wt 0 100 2.86 5.81

Table 1: Main properties of test fuels and additives

controlled by varying the ratio of the dilution air flow rate to
that of the raw exhaust. The secondary dilution ratio was 10
and was kept constant throughout the study, providing the
overall dilution ratios of around 50–70.
Particulate matter measurements
Particle number distribution measurements were made by
a scanning mobility sizer (SMPS, model 3934, TSI Inc.,
USA), consisting of a differential mobility analyser (model
3071), condensation particle counter (model 3010) and elec-
trical low-pressure impactor (ELPI, Dekati Ltd.). As Fig 1
shows, the operational scheme for the instruments was cho-
sen to operate simultaneously, which not only significantly
increased system reliability, but also made it more flexible
with regard to the PM parameters analysed. In current study
a real-time 12-channel ELPI38, covering a wide particle size
range from 7nm to 10μm to monitor the stability of PM emis-
sions during measurements, while SMPS39 provided the main
number size distributions as it has a much higher particle-size
resolution. The flow settings for SMPS were 0.3 and 3 l/min
for polydisperse aerosol and sheath flow respectively, and
the up and down scanning times were 120 and 45sec. For
the experiment, the analysed size window of 0.014–0.6μm
was chosen as optimum to cover the number-size distribution
spectra in all operational modes for all the fuels tested.
The total suspended particulate mass concentration was
determined from the gravimetric analysis. A sample of
diluted exhaust was transported through flexible conductive
tubing from the dilution unit by means of a vacuum pump at

Fig 2: Comparison of particulate number size distributions for various engine operating conditions and various fuels
at PDT=400/30°C

33 Journal of Marine Engineering and Technology      Volume 12  No 3 September 2013

Ushakov_JMET_Sep.indd 33 06/11/13 6:12 PM

 Effects of high sulphur content in marine fuels on particulate matter emission characteristics
Operating mode 2 3 4 5
Load, % 10 25 50 75
Power, kW 20 50 100 150
Engine speed, rpm 1080 1080 1080 1080
Table 2: Test modes with corresponding engine operating parameters
steady flow rate to a particulate matter filter loading station,
where particles were collected on Pall Corp. (USA) 47mm
Teflon-coated glass fiber filters. Each sampling was carried
out over a timed period of between 20 and 35min, depend-
ing on engine load conditions. During this time the flow rate
through the filter remained constant at a value between 10 and
15 l/min, in order to fulfill the maximum filter-face velocity
requirements.40 The flow rate was provided by a leak-proof
vacuum pump regulated by an external frequency controller.
Before and after sampling, all filters were equilibrated for 24h
in an environment-controlled weighing chamber whose rela-
tive humidity and temperature were maintained in the range
of 42±3% and 25±1°C respectively41. This was done since
sulphuric acid is inherently hygroscopic, so control over the
take-up of water and the hydration of the acid is absolutely
critical, especially when fuels with high sulphur content
are being used. Finally, the total mass was determined by
­weighing the loaded filters on a Mettler AE 163 balance with
a sensitivity of 0.1mg.
Results and Discussion
PM number size distributions
The particulate matter number size distribution results for
all studied fuels are presented in Fig 2 for different engine
operating conditions and at two settings of PDT. All results
are plotted on a log-log scale and in all cases the distribu-
tion is the average of four to six distribution measurements.
PM number distributions showed a characteristic bimodal
shape for all fuel types at intermediate speed (1080rpm) low
load conditions (20kW/10% of maximum engine load) with
a typical diesel accumulation mode of around 70–130nm.
This mode was independent of fuel sulphur content and is
believed to consist mainly of carbonaceous agglomerates
(soot). Some sulphuric acid with associated bound water
was also present in the accumulation mode in the form
of a thin layer formed on soot particles by heterogeneous
nucleation processes7, 15 as indicated by the heat treatment
(PDT=400°C) employed (see Figs 2–4). Nevertheless, most
of the fuel sulphur still ended up as separate nuclei formed
through the homogeneous nucleation of sulphuric acid when
nucleating species exceeded their supersaturation ratio dur-
ing rapid dilution6 and comprised a pronounced nucleation
mode below 50nm. In many studies6, 42–45 homogeneous
nucleation process has been linked only with lack of soot,
which acts as a ‘sink’ for the condensation and/or adsorp-
tion of semivolatile materials such as sulphuric acid8, but as
this study shows, the nucleation process is also correlates
closely with high sulphur content. We can also see that the
Volume 12  No 3 September 2013       Journal of Marine Engineering and Technology
Ushakov_JMET_Sep.indd 34
9 10 11 12 13
60 40 20 8 0
168 112 56 22 0
1800 1800 1800 1800 750
nucleation mode diameter increases with fuel sulphur con-
tent, from less than 1 nm for 0.05% S fuel to around 20–30
and 30–40nm respectively for 2% and 4% S fuels. This can
be explained by the fact that as more nucleation particles
are formed, the more surface area they could provide for
the condensation of such sulphuric acid as was still volatile.
Moreover, in the cases of 2% and 4% S fuels, much more
vapour-phase semivolatile hydrocarbons and sulphuric acid
are available for condensation, thus reducing the growth of
nucleated particles. Nucleation is also very dependent on
dilution conditions, which can substantially promote nano-
particle formation.8, 46 Unburned hydrocarbons together with
lubrication oil sulphur and metallic ash can also contribute
to the nucleation peak under low load conditions. Although
their contribution might be significant when low sulphur
fuel47 such as 0.05% S MGO is being tested, in the cases
of our 2% and 4% S fuels, a contribution of lubrication
oil containing 0.6% S can be regarded as negligible, as the
consumption of oil compared to that of fuel is rather small.
Particle number size distributions for all test fuels in
mode 5 (1080rpm and 150kW) were unimodal, with the only
typical accumulation peak in the range of 70–130nm. These
­distributions were almost entirely independent of sulphur
content, with the particle mean count median diameter (CMD)
value being slightly higher for 2 and 4% S fuels (Fig 4). The
‘hot’ dilution displayed only a minor effect of these particles
(Fig 3), which confirms that they consist almost completely
of soot. Accumulation-mode particle concentration was found
to increase with load at intermediate speed, which can be the
result of an increased amount of injected fuel and associated
more locally rich combustion zones formed inside the cylin-
ders11, which are mainly responsible for higher production
rates of soot particles.
Under full-speed (1800rpm) mode 12 (22kW/8% of
maximum engine load) conditions the observed particle size
distributions were bimodal, with the accumulation-mode
peak lying around 50–90nm and the nucleation-mode peak
somewhere below 20nm. The actual nucleation mode peak is
‘hidden’ as it exists in the range below the lower sensitivity
limit of the instrument, ie, below 14nm. Similarly, the mode
9 case (165kW/60% load) revealed a unimodal shape of PM
number distributions with the expected accumulation mode
of around 50–90nm. In contrast to the case of intermediate
speed, almost no change in accumulation mode concentra-
tion was measured when we switched from low to high load,
ie, from 8% to 60% load. This can be explained by the very
different air/fuel ratios employed at rated and full speed, with
air-fuel ratio values being higher at full speed, thus minimis-
ing the formation of locally rich zones responsible for higher
soot production rates.
34
06/11/13 6:12 PM
 Effects of high sulphur content in marine fuels on particulate matter emission characteristics

Fig 3: Effect of fuel sulphur content on total particle concentration and percentage of nanoparticles (<50nm) under various load
and speed conditions at PDT=400/30°C

Fig 4: Mean count median diameter calculated for all fuels and test modes at PDT=400/30°C

35 Journal of Marine Engineering and Technology      Volume 12  No 3 September 2013

Ushakov_JMET_Sep.indd 35 06/11/13 6:12 PM

 Effects of high sulphur content in marine fuels on particulate matter emission characteristics
Under low-load conditions, at both intermediate and full
speed, ie, for modes 2 and 12, the influence of increase in
PDT on nucleation mode particle formation appeared to be
moderate for all fuels (Fig 2), although it resulted both in a
certain reduction of total particle concentration (Fig 3) and a
shift to smaller CMD values (Fig 4). This can be explained
by an increase in the vapour pressures of volatile species
slowing down the nucleation rate when PDR is increased.46,
48
However, even at PDT=400°C, the observed nucleation
mode did not completely disappear, which might suggest that
these particles were solid and were originated from lube oil
components14, 49, which is a reasonable explanation for 0.05%
S fuel. Alternatively, an excessively low primary dilution ratio
may have been employed, with the result that the dew-point
of sulphuric acid was not reached, so that supersaturation still
occurred. The latter explanation seems to be very likely in the
case of high-sulphur fuels that we used during the study, and it
has already been reported in the literature.25 A further consid-
eration is that the type of diluter and the dilution set-up also is
vital for nuclei-mode particle formation34, so we need to bear
in mind that the primary porous-tube diluter used in this study,
is known to conditions not favorable for nucleation, mainly
because of rather slow and imperfect mixing, which is a result
of how dilution takes place. However, stronger nucleation may
still occur in the secondary ejector diluter.35
It should also be emphasised that a shift to smaller mode
diameters was observed for all experimental fuels when from
intermediate to full speed. This was true for both nucleation-
and accumulation-mode PM, as shown in Fig 4. This fact can
probably be linked to higher exhaust flow rates caused by the
increase in engine speed, which means that particles simply
have a shorter residence time to grow to bigger sizes. Mean
CMD values are dominated by nucleation-mode particles at
low loads and by accumulation-mode PM at medium to high
loads. A certain effect of PDT can also be seen. The differences
in mean CMDs for each mode are rather pronounced for all the
fuels tested, although it is difficult to draw form conclusions,
due to the high standard error observed in some cases.
As Fig 3 shows, the total number of particles in the size
range of 14–600nm was much higher for 2% and 4% S fuels
than for conventional MGO low-load and idle conditions.
This is mainly due to a pronounced increase in the number
of nanoparticles6 for these load conditions (Fig 3), with most
of the particles being formed during the dilution process. In
certain cases for 2% for 4% S fuel, nanoparticles comprise up
to 95% of the total number of PM. This is a further example
of the critical importance of dilution parameters. Under low-
load conditions, the total PM concentration and the percent-
age of nanoparticles need to be considered carefully, as PM
concentration at a lower analyser cutoff is still high, and in
some cases even increases.
PM mass concentrations
The total PM mass was determined by gravimetric analysis
under various operating conditions for all three fuels and the
results are shown in Fig 5 for different settings of PDT. A set
of slightly lower power test points was chosen for particle mass
sampling at high loads to prevent potential artefacts due to
unstable engine operation caused by water-brake limitations. In
Volume 12  No 3 September 2013       Journal of Marine Engineering and Technology
Ushakov_JMET_Sep.indd 36
all cases, PM mass increased with in line with the increase of
sulphur content in fuel, a finding that agrees well with earlier
studies.50 This result is even more pronounced under ‘cold’
dilution conditions, which known to favour nucleation and/or
condensation of sulphuric acid with associated bound water.34,
51
The contribution of nuclei mode particles to total mass is nor-
mally below 20% for typical on-road vehicle fuels9, but in the
current case of 2% and 4% S fuels nucleation mode contribu-
tion to PM may exceed this value. On the other hand, the effect
of load on PM mass appeared to be even more pronounced
and sometimes, as in the 1080rpm high-load case, it dominates
over the effect of fuel type. This observation should be related
to accumulation-mode PM number concentrations, which
increase with load and are known to make up most of the PM
mass.7 The change in engine speed probably has only a modest
effect, unless it leads to changes in accumulation- (soot) mode
particulate matter concentration.
In addition, PM mass concentrations were calculated from
the size distributions measured by ELPI. We assumed spheri-
cal particles with a unit density (1g/cm3) for the calculation.
Only the lowest seven stages were taken into consideration,
in order to prevent the coarse-mode artefact reported in the
­literature.52 Essentially, a fairly good correlation between
gravimetrically measured PM mass and one calculated from
ELPI data was found for all the measurements (Fig 6) under
‘hot’ dilution conditions. A somewhat higher degree of
uncertainty was observed under low load conditions, where
significant quantities of vapour-phase organic compounds,
typical for such operating conditions, can simply pass straight
through the filter.28 Moreover, some low-boiling-point com-
pounds can be temporarily deposited on the filter and subse-
quently re-evaporate.53 Capturing these compounds may well
improve the agreement between measured and calculated
PM mass, although this requires additional inventory like
sorbent or a trap. The most significant source of error prob-
ably arises from the assumption of unit density, applied to all
particles during PM mass calculation. This assumption could
be true for droplet-shaped structures such as nucleation-mode
­particles, but not for soot particles, which are known to have
fractal densities that decrease as particle size increases.21, 54
In addition, the relatively low sensitivity of the balance used
to weigh the filters may also have contributed to measure-
ment uncertainty, particularly under low-load conditions.
Nevertheless, we believe that calculating PM mass concen-
trations from ELPI data could be a rather good and reli-
able method for preliminary assessment of particulate mass,
although more thorough studies are needed on this topic.
CONCLUSIONS
The paper has presented results on the effect of high sulphur
content in marine fuels on particle emission characteristics, as
measured on diesel engine exhaust, and revealed a high cor-
relation between fuel sulphur levels and the number and mass
of emitted particulates. The nucleation-mode PM appeared to
be most affected, as it mainly consist of condensed/nucleated
hydrocarbon and sulphur compounds that dominate under
low-load conditions. These particles comprise most of the
total PM number, and thus affect mean CMD value. The accu-
mulation mode was almost entirely independent of sulphur
36
06/11/13 6:12 PM
 Effects of high sulphur content in marine fuels on particulate matter emission characteristics

Fig 5: Effect of sulphur level in fuel on PM mass emissions, as determined by gravimetric analysis, under various engine load and
speed conditions when sampling at PDT=400/30°C

Fig 6: Particle mass comparison: measured from gravimetric analysis versus calculated from ELPI number distributions at ‘hot’
dilution (PDT=400°C)

37 Journal of Marine Engineering and Technology      Volume 12  No 3 September 2013

Ushakov_JMET_Sep.indd 37 06/11/13 6:12 PM

 Effects of high sulphur content in marine fuels on particulate matter emission characteristics
content in fuel, as it is thought to consist of soot agglomer-
ates formed during combustion, which are affected by engine
load and speed conditions. This mode represents most of the
particle mass, although a pronounced increase of PM mass
was observed when the level of sulphur in fuel was increased.
The effect of PDT on size distributions was found to be
fairly moderate for the nucleation mode and, as expected, was
negligible for the soot mode. Even raising PDT from 30°C to
400°C, which increased the vapour pressures of volatile species
and significantly slowed down nucleation, did not eliminate the
nucleation mode. This observation for high-sulphur fuels can be
explained by insufficient primary dilution ratio, which did not
allow to exceed sulphuric acid due point. If the latter is required,
the higher primary dilution ratios (above 12–15) should be used.
This study could be improved and extended by using
a wider range of sulphur dopants (instead of just one) that
should be added to fuel in proportion to the content of real
sulphur-bearing compound groups that they represent.
ACKNOWLEDGEMENTS
The authors gratefully acknowledge financial support from
the Research Council of Norway, Det Norske Veritas (DNV),
Statoil, FuelTech Solutions and Teekay under a KMB project.
REFERENCES
1. Dockery D, Pope CA, Xu X, Spengler J, Ware J, Fay
M, Ferris B and Speizer F. 1993. An association between air
pollution and mortality in six US cities. New England Journal
of Medicine 329: 1753–1759.
2. Pope III CA, Thun MJ, Namboodiri MM, Dockery KS,
Evans JS, Speizer FE and Heath Jr. CW. 1995. Particulate air
pollution as a predictor of mortality in a prospective study of
US adults. American Journal of Respiratory and Critical Care
Medicine 151: 669–674.
3. Pope III CA. 2000. Epidemiology of fine particulate air
pollution and human health: Biologic mechanisms and who’s
at risk? Environmental Health Perspectives 108 (Suppl.):
713–723.
4. Oberdörster G. 2000. Toxicology of ultrafine particles:
In vivo studies. Philosophical Transactions of the Royal
Society A: Mathematical, Physical and Engineering Sciences
258: 2719–2740.
5. Forsberg B, Hansson H-C, Johansson C, Areskoug H,
Persson K and Järvholm B. 2005. Comparative health impact
assessment of local and regional particulate air pollutants in
Scandinavia. Ambio 34: 11.
6. Ristovski ZD, Jayaratne ER, Lim M, Ayoko GA and
Morawska L. 2006. Influence of diesel fuel sulfur on nano-
particle emissions from city buses. Environmental Science
and Technology 40: 1314–1320.
7. Kittelson DB. 1998. Engines and nanoparticles: a
review. Journal of Aerosol Science 29: 575–588.
8. Abdul-Khalek IS, Kittelson DB and Brear F. 1998.
Diesel trap performance: particle size measurements and
trends. SAE Paper 982599.
9. Kittelson DB, Arnold M and Watts WF. 1999. Review
of diesel particulate matter sampling methods. Final Report.
University of Minnesota: Minneapolis, MN.
Volume 12  No 3 September 2013       Journal of Marine Engineering and Technology
Ushakov_JMET_Sep.indd 38
10. Kittelson DB, Watts WF and Johnson J. 2002. Diesel
aerosol sampling methodology. Final Report # CRC-E43.
University of Minnesota: Minneapolis, MN.
11. Tobias HJ, Beving DE and Ziemann PJ. 2001.
Chemical analysis of diesel engine nanoparticles using a
nano-DMA/thermal desorption particle beam mass spectrom-
eter. Environmental Science and Technology 35: 2233–2243.
12. Sakurai H, Tobias HJ, Park K, Zarling D, Docherty
KS, Kittelson DB, McMurry PH and Ziemann PJ. 2003.
On-line measurements of diesel nanoparticle composition,
volatility, and hygroscopicity. Atmospheric Environment 37:
1199–1210.
13. Rönkkö T, Virtanen A, Kannosto J, Keskinen J, Lappi
M and Pirjola L. 2007. Nucleation mode particles with a non-
volatile core in the exhaust of a heavy duty diesel vehicle.
Environmental Science and Technology 41: 6384–6389.
14. De Filippo A and Maricq MM. 2008. Diesel nuclea-
tion mode particles: semivolatile or solid? Environmental
Science and Technology 42: 7957–7962.
15. Shi JP and Harrison RM. 1999. Investigation of
ultrafine particle formation during diesel exhaust dilution.
Environmental Science and Technology 33: 3730–3736.
16. Yost DM, Montalvo DA and Frame EA. 1996. US
Army investigation of diesel exhaust emissions using JP-8
fuels with varying sulfur content. SAE Paper 961981.
17. Daniels TL, McComick RL, Graoski MS, Carlson PN,
Rao V and Rice GW. 1996. The effect of diesel sulfur content
and oxidation catalysts on transient emissions at high altitude
from a 1995 Detroit Diesel series 50 urban bus engine. SAE
Paper 961974.
18. Wall JC, Shimpi SA and Yu ML. 1987. Fuel sulfur
reduction for control of diesel particulate emissions. SAE
Paper 872139.
19. Wall JC and Hoekman SK. Fuel composition effects on
heavy duty diesel particulate emissions. SAE Paper 841364.
20. Bagley ST, Baumgard KJ, Gratz LD, Johnson JJ and
Leddy DG. 1996. Characterization of fuel and aftertreatment
devices on diesel emissions. HEI Research Report No. 88.
Health Effects Institute: Boston, MA.
21. Kasper A, Aufdenblatten S, Forss A, Mohr M and
Burtscher H. 2007. Particulate emissions from a low-speed
marine diesel engine. Aerosol Science and Technology 41:
24–32.
22. Moldanova J, Fridell E, Popovicheva O, Demirdjian B,
Tishkova V, Faccinetto A and Fosca C. 2009. Characterisation
of particulate matter and gaseous emissions from a large ship
engine. Atmospheric Environment 43: 2632–2641.
23. Sarvi A, Lyyränen J, Jokiniemi J and Zevenhoven R.
2011. Particulate emissions from large-scale medium-speed
diesel engines: 1. Particle size distribution. Fuel Processing
Technology 92: 1855–1861.
24. Ushakov S, Valland H, Nielsen JB and Hennie E.
2012. Particulate emission characteristics from medium-
speed marine diesel engines. Proceedings of PACIFIC 2012
International Maritime Conference. 31 January – 2 February
2012, Sydney, Australia.
25. Ristimaki J, Hellen G and Lappi M. 2010. Chemical
and physical characterization of exhaust particulate matter
from a marine medium speed diesel engine. Paper 73. CIMAC
Congress 2010, Bergen, Norway.
38
06/11/13 6:12 PM
 Effects of high sulphur content in marine fuels on particulate matter emission characteristics
26. Eyring V, Kohler HW, van Aardenne J and Lauer A.
2005. Emissions from international shipping: 1. The last 50
years. Journal of Geophysical Research 110: D17305.
27. IMO. 1998. International Maritime Organisation
(IMO). 1998 Annex VI of MARPOL 73/78 Regulations for the
Prevention of Air Pollution from Ships. MPG Books Ltd., UK.
28. Eastwood P. 2008. Particulate emission from motor
vehicles. John Wiley & Sons Ltd., Chichester, UK. 493 pp.
29. EEC. 1988. European Economic Community Directive
88/77. EEC, Journal Official L36.
30. Kittelson DB and Johnson JH. 1991. Variability in
particle emission measurements in the heavy duty transient
test. SAE Paper 910738.
31. Baron PA and Willeke K. 2001. Aerosol Measurement:
Principles, Techniques and Applications 2nd edition. John
Wiley & Sons Inc., Hoboken, New Jersey. 1131 pp.
32. Ushakov S, Valland H, Nielsen JB and Hennie E.
2013. Particle size distributions from heavy-duty diesel
engine operated on low-sulfur marine fuel. Fuel Processing
Technology 106: 350–358.
33. Wierzbicka A, Lillieblad, L, Pagels J, Strand M,
Gudmundsson A, Gharibi A, Swietlicki E, Sanati M and
Bohgard M. 2005. Particle emissions from district heating
units operating on three commonly used biofuels. Atmospheric
Environment 39: 139–150.
34. Mathis U, Ristimaki J, Mohr M, Keskinen J,
Ntziachristos L, Samaras Z and Mikkanen P. 2004. Sampling
conditions for the measurement of nucleation mode parti-
cles in the exhaust of a diesel vehicle. Aerosol Science and
Technology 38: 1149–1160.
35. Lyyränen J, Jokiniemi J, Kauppinen EI, Backman U
and Vesala H. 2004. Comparison of different dilution methods
for measuring diesel particle emissions. Aerosol Science and
Technology 33: 239–260.
36. Lüders H, Kruger M, Stommel P and Luers B. 1998.
The role of sampling conditions in particle size distribution
measurements. SAE Paper 981374.
37. Maricq MM, Chase RE, Podsiadlik DH and Vogt R.
1999. Vehicle exhaust particle size distributions: A compari-
son of tailpipe and dilution tunnel measurements. SAE Paper
1999-01-1461.
38. Keskinen J, Pietarinen K and Lehtimäki M. 1992.
Electrical low pressure impactor. Journal of Aerosol Science
23: 353–360.
39. Knudson EO and Whitby KT. 1975. Aerosol classifi-
cation by electric mobility: apparatus, theory, and applica-
tion. Journal of Aerosol Science 6: 443–451.
40. ISO. 2006. International Standard 8178-1, Reciprocating
internal combustion engines – Exhaust emission measurement.
Part 1: Test-bed measurement of gaseous and particulate
exhaust emissions. 2nd edition, Geneva, Switzerland.
41. Opris CN, Gratz LD, Bagley ST, Baumgard KJ, Leddy
DG and Johnson JH. 1993. The effects of fuel sulfur concen-
tration on regulated and unregulated heavy-duty diesel emis-
sions. SAE Paper 930730.
42. Armas O, Ballesteros R and Gomez A. 2008. The effect
of diesel engine operating conditions on exhaust particle size
distributions. Proceedings of the Institution of Mechanical
Engineers: Part D, Journal of Automobile Engineering 222:
1513–1525.
39 Journal of Marine Engineering and Technology      Volume 12  No 3 September 2013
Ushakov_JMET_Sep.indd 39
43. Baumgard KJ and Johnson JH. 1996. The effect of fuel
and engine design on diesel exhaust particle size distribu-
tions. SAE Paper 960131.
44. Maricq MM, Chase RE, Xu N and Laing PM. 2002.
The effects of the catalytic converter and fuel sulfur level on
motor vehicle particulate matter emissions: light duty diesel
vehicles. Environmental Science & Technology 36: 283–290.
45. Johnson JH, Kittelson DB and Watts WF. 2009. The
Effect of Federal Fuel Sulfur Regulations on In-Use Fleets:
On-Road Heavy-Duty Source Apportionment. Environmental
Science & Technology 43: 5358–5364.
46. Abdul-Khalek IS, Kittelson DB and Brear F. 1999.
The influence of dilution conditions on diesel exhaust particle
size distribution measurements. SAE Paper 1999-01-1142.
47. Vaaraslahti K, Virtanen A, Ristimaki J and Keskinen
J. 2004. Nucleation mode formation in heavy-duty diesel
exhaust with and without a particulate filter. Environmental
Science & Technology 38: 4884–4890.
48. Ushakov S, Valland H, Nielsen JB and Hennie E. 2012.
Effects of Dilution Conditions on Diesel Particle Size Distribution
and Filter Mass Measurements in Case of Marine Fuels. Fuel
Processing Technology, submitted for publication in August 2012.
49. Lähde T, Rönkkö T, Virtanen A, Solla A, Kytö M,
Söderström C and Keskinen J. 2010. Dependence between
Nonvolatile Nucleation Mode Particle and Soot Number
Concentrations in an EGR Equipped Heavy-Duty Diesel Engine
Exhaust. Environmental Science & Technology 44: 3175–3180.
50. Lee R, Pedley J and Hobbs C. 1998. Fuel quality
impacts on heavy duty diesel emissions - a literature review.
SAE Paper 982649.
51. Khalek IA, Kittelson DB and Brear F. 2000.
Nanoparticle growth during dilution and cooling of diesel
exhaust: experimental investigation and theoretical assess-
ment. SAE Paper 01-0515.
52. Maricq MM, Podsiadlik DH and Chase RE. 2000.
Size distributions of motor vehicle exhaust PM: A comparison
between ELPI and SMPS measurements. Aerosol Science and
Technology 33: 239–260.
53. Samara C. 1995. Analysis of organic matter. In
Airborne Particulate Matter, Volume 4, Part D. Kouimtzis T
and Samara C. (eds.), Springer. 233–252 pp.
54. Burtscher H. 2005. Physical characterization of par-
ticulate emissions from diesel engines: a review. Journal of
Aerosol Science 36: 896–932.
NOMENCLATURE
CMD count median diameter
DMDS dimethyl disulphide
ELPI electrical low-pressure impactor
IMO International Maritime Organization
MDE marine diesel engine
MGO marine gas oil
PDT primary dilution temperature
PM particulate matter
SMPS scanning mobility particle sizer
06/11/13 6:12 PM