400 Commonwealth Drive, Warrendale, PA 15096-0001 U.S.A. Tel: (724) 776-4841 Fax: (724) 776-5760 Web: www.sae.

org
2005-01-0190
French Program on the Impact of Engine
Technology on Particulate Emissions,
Size Distribution and Composition
Heavy Duty Diesel Study
Stphane Raux and Laurent Forti
Institut Franais du Ptrole
S. Barbusse and G. Plassat
Agence de l'Environnement et de la Matrise de l'Energie
L. Pierron
Renault VI Powertrain
R. Monier and J. C. Momique
PSA Peugeot-Citron
C. Pain, B. Dionnet, E. Zervas, P. Rouveirolles and P. Dorlhene
Renault
Reprinted From: Emissions Measurement and Testing 2005
(SP-1941)
SAE TECHNICAL
PAPER SERIES
The Engineering Meetings Board has approved this paper for publication. It has successfully completed
SAEs peer review process under the supervision of the session organizer. This process requires a
minimum of three (3) reviews by industry experts.
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or
transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise,
without the prior written permission of SAE.
For permission and licensing requests contact:
SAE Permissions
400 Commonwealth Drive
Warrendale, PA 15096-0001-USA
Email: permissions@sae.org
Tel: 724-772-4028
Fax: 724-772-4891
For multiple print copies contact:
SAE Customer Service
Tel: 877-606-7323 (inside USA and Canada)
Tel: 724-776-4970 (outside USA)
Fax: 724-776-1615
Email: CustomerService@sae.org
ISSN 0148-7191
Copyright 2005 SAE International
Positions and opinions advanced in this paper are those of the author(s) and not necessarily those of SAE.
The author is solely responsible for the content of the paper. A process is available by which discussions
will be printed with the paper if it is published in SAE Transactions.
Persons wishing to submit papers to be considered for presentation or publication by SAE should send the
manuscript or a 300 word abstract to Secretary, Engineering Meetings Board, SAE.
Printed in USA
ABSTRACT
An extensive research program involving the French
passenger car and heavy-duty (HD) vehicles
manufacturers, sponsored by ADEME and realized by
IFP, aimed to characterize in terms of size and
composition the particulate emitted by the different
engine technologies currently or soon available. The
impact of engine settings and fuel composition was also
studied. Numerous information was collected in this HD
study revealing that fuel composition and particularly
non-conventional fuels and engine settings strongly
impact the particulate concentration and size distribution.
Nucleation is likely to occur when there is less adsorption
matter, for instance when post-injection is used or EGR
is removed. Particulate composition, particularly PAH
and sulfates content, is weakly bound to the size. Mineral
elements distribution depends on their origin, lubrication
oil or engine wear.
INTRODUCTION
Internal combustion engine technology has encountered
a fantastic evolution during last decade due to the
application of more and more stringent emission
regulations. Thus both personal and heavy duty vehicles
composing the current European fleets are equipped with
engines using various technologies. The fuels presently
used meet the 2000 specifications; however, the major
part of the vehicles now on the road will still be used after
2005 when new fuel specifications have to be observed.
Concerning Diesel particulate emissions, the regulation
to be complied with is a mass per energy produced (HD)
or per run kilometer for the light-duty vehicles (LD), with
no consideration for particulate size distribution. However
recent studies suggest that particulate toxicity is highly
related to their diameter and specific surface
1,2
.
Particulate are also emitted by indirect injection gasoline
engines but in a far lower concentration due to an
homogeneous mix of air and fuel. New stratified direct
injection engines may nevertheless not follow this trend.
Sponsored by ADEME (French Agency for Environment
and Energy Management), PSA Peugeot-Citron,
Renault, RVI and the Institut Franais du Ptrole (IFP),
the aim of the Primequal French research program is to
characterize the particulate emissions of engine
technologies representative of the present European
fleet, with the current used fuels. Most recent engines
are also tested with a fuel whose specifications meet the
future 2005 standard. Two techniques are used to
characterize the exhaust aerosol, the SMPS (Scanning
Mobility Particle Sizing) and a LPI (Low Pressure
Impactor) sampling. Physical and chemical analyses of
particulate sampled by the LPI bring further knowledge of
particulate composition.
The results presented hereafter are those obtained on
the heavy-duty engines. Three engines were tested, all
manufactured by Renault VI : MIDR 62045 Euro II, MIDR
60226 Euro III (DCI6), and a single-cylinder prototype
engine preceding Euro IV standard.
2005-01-0190
French Program on the Impact of Engine Technology on
Particulate Emissions, Size Distribution and Composition
Heavy Duty Diesel Study
Stphane Raux and Laurent Forti
Institut Franais du Ptrole
S. Barbusse and G. Plassat
Agence de l'Environnement et de la Matrise de l'Energie
L. Pierron
Renault VI Powertrain
R. Monier and J. C. Momique
PSA Peugeot-Citron
C. Pain, B. Dionnet, E. Zervas, P. Rouveirolles and P. Dorlhene
Renault
Copyright 2005 SAE International
EXPERIMENTAL MEANS
ENGINES
The main characteristics of the three engines tested are
listed in table 1.
Euro II Euro III Euro IV
Designation
MIDR
62045
DCI6
Single
cylinder
120-45
Displacement
(l)
9.84 6.18 1.64
Nb cylinders 6 6 1
Valve/cyl. 2 2 4
Comp. Ratio 17 : 1 17 : 1 16 : 1
Bore (mm) 120 102 120
Stroke (mm) 145 126 145
Max. power
(kW) at (rpm)
190
2 100
195
2 400
40
2 000
Max. torque
(N.m) at (rpm)
1 070
1 400
900
1 200
250
1 100
Injection type In-line Common rail Common rail
EGR No Cooled Cooled
Table 1 : Engines characteristics
RUNNING POINTS
The selected test conditions are part of the European
Steady-state Cycle (ESC) ensuring a wide variation of
equivalence ratio and exhaust gas temperature. The
main characteristics of these points are mentioned in the
table 2. A, B and C refer to three engine rotation speeds,
and 25, 50 75 and 100 to the percentage of maximum
load at the corresponding rev. For each engine the three
revs are regularly spread out in a specific rev range. The
lower edge N1 is the rotation speed, slower than the
maximum power rev, giving half the maximum power.
The upper edge N2 is the engine speed, faster than the
maximum power rev, giving 70% of the maximum power.
This is shown in the chart 1.
Chart 1 : Definition of the ESC engine test speeds
Engine
Euro
Rev
(rpm)
Torque
(N.m)
EGR
(%)
A/F
PM
(g/kW.h)
exhaust
T (C)
II 1 260 955
1
- 27 0.06 537
III 1 475 885 0 25 0.09 480
IV 1 250 250 10 26 0.13 534
II 1 580 520 - 41 0.08 400
III 1 850 425 8.2 30 0.05 375
IV 1 600 120 10 30 0.15 463
II 1 580 790 - 34 0.07 480
III 1 850 640 4.8 28 0.05 410
IV 1 600 180 11 27 0.07 505
II 1 900 240 - 57 0.12 300
III 2 225 193 14 45 0.13 300
IV 1 850 48 17 45 0.16 312
II 1 900 860
1
- 34 0.07 515
III 2 225 757 11 27 0.09 435
IV 1 850 190 17 25 0.18 530
C100
A100
B50
B75
C25
1
: 90 % max. load only for power loss with WFE (Water-Fuel
Emulsion)
Table 2 : Test conditions
The options chosen here for Euro IV are EGR and a
Diesel particulate filter what explain why the engine-out
particulate emissions of the Euro IV engine are not better
than those of the two other engines. It must be kept in
mind that most of European truck manufacturers chose
the Selective Catalytic Reduction for Euro IV (NOx
reduction on a catalyst by urea injection in the exhaust
gases) that allows engine settings giving engine-out
particulate emissions complying with Euro IV regulations
without any filter.
The influence of the main settings are estimated on two
running points. Thus, depending on the engine
technology, EGR is removed, injection pressure is raised
by 100 bar, injection timing is delayed by 2 degrees and
a pilot or a post injection is activated or deactivated (Euro
III & IV). The standard settings of the Euro III engine use
a post-injection. On the Euro II engine, only the injection
timing can be changed by advancing the static timing of
the injection pump up to ten degrees (see chart 2).
Chart 2 : Injection timing on Euro II engine
FUELS
The properties of the fuels used for the engine tests are
listed in table 3 and 4. The Euro2000 Diesel fuel is
commonly used for all engines, while the Swedish City
Fuel class 1 (sulfur content less than 10 ppm) is only
tested with Euro III and Euro IV engines and the water-in-
fuel emulsion (WFE) use is restricted to the Euro II
engine. As this emulsion contains about 15% water, the
maximum power that can be obtained is lower. With
Euro II engine, in order to compare fuels at the same
power, full load tests are performed at the maximum
power obtained with the emulsion.
Euro2000 Swedish
City Fuel
Water-in-
Fuel
Emulsion
Density (kg/m
3
) at
15C
NF EN ISO 12185/96
841.8 812.0 856.3
Cetan index
ASTM D613/86
50.8 54.0 51.6
Sulfur (ppm mass)
ASTM D2622
335 4 245
Kinematic viscosity at
40C (mm/s)
NF EN ISO 3104/96
2.962 1.918 3.319
Atmospheric distillation
ISO 3405/88
IP (C) 179.5 204.0 -
T5% (C) 204.5 217.5 -
T50% (C) 282.5 232.0 -
T95% (C) 361.5 256.5 -
FP (C) 363.5 262.0 -
Lower Heating Value
(kJ/kg)
NFM07-30
43 210 43 520 37 890
H/C
IFP-9320
1.869 1.990 1.842*
* : hydrogen content of water deducted
Table 3 : Physical properties of fuels
(%m) Euro2000 Swedish
City Fuel
WFE
ASTM D2425 modified
paraffins 37.6 37.1 -
naphtenes 36.1 62.1 -
non condensed 21.4 36.3 -
condensed 14.7 25.8 -
mono aromatics 18.9 0.6 -
alkylbenzenes 10.8 0.4 -
indanes & tetralines 6.3 0.2 -
indenes 1.8 0 -
di aromatics 7.0 0.2 -
naphtalenes 4.3 0.2 -
acenaphtenes & diphenyles 1.7 0.0 -
fluorenes & acenaphtylenes 1.0 0.0 -
tri aromatics (anthracenes
& phenanthrenes)
0.4 0.0 -
poly-aromatics 0.0 0.0 -
Sulfur components 0.0 0.0 -
Table 4 : Chemical properties of fuels
PARTICULATE SAMPLING AND GLOBAL ANALYSES
Particulate are sampled by means of a micro dilution
tunnel on two 47 mm diameter fiberglass filters
(PALLFLEX T60A20). Total exhaust particulate flow is
calculated knowing the sampled gas flow and the CO
2
concentration, thus the dilution ratio. Soot loaded filters
are thermally and hygrometrically stabilized before
weighing. A second weighing after a 3 hours heating at
210C leads to the volatile organic mass fraction.
The smoke level is measured by a Pierburg PR-1, which
optically determines the opacity of a filter blackened by
the exhaust gases flowing through it.
PARTICULATE SIZE DETERMINATION AND
ANALYSES BY SIZE
Particulate size determination is performed using the
SMPS technique and a TSI apparatus. A 3071
Differential Mobility Analyzer (DMA) is coupled to a
3022A Condensation Nuclei Counter. The exhaust gases
are diluted 10 times with filtered air inside the DMA. With
the 0.0457 cm impactor located at the inlet of the 3071,
the selected flows in the DMA allow the particulate sizing
over the 10 nm-470 nm diameter range. Primary dilution
and sampling use the same probe as that devoted to the
particulate collection on fiberglass filters for mass
emission measurements.
Thanks to a Dekati Low Pressure cascade Impactors
(LPI), the exhaust particulate size spectrum is split into
13 diameter ranges from 32 nm for a 100 mbar absolute
outlet pressure (see Table 5). The sampled gases are
first diluted with dried and filtered air, very close to the
sampling probe. The probe, which is different than the
one used for SMPS sampling due to the high flow
required by the impactors, is made of a simple tube
located in the middle of the exhaust stream, facing the
incoming gases. Contrary to the ELPI, the LPI allows the
use of fiberglass and polycarbonate filters to collect and
weigh the particulate and then further chemical analyses.
Impaction plate
50% cut-off diameter
(m)
P : 100 mbar
1 0.032
2 0.064
3 0.110
4 0.179
5 0.275
6 0.421
7 0.68
8 1.05
9 1.71
10 2.60
11 4.21
12 7.03
13 10.8
Table 5 : LPI cut-off diameters
The LPI samplings are only performed on the B50
running point, with the Euro2000 fuel.
PIXE analysis (Particle Induced X-ray Emission) is used
to measure the mineral elements content of the
particulate. A proton beam interacts with target atoms
resulting in the emission of an X-ray whose energy
indicates the nature of the target element. The surface
explored is a 15 mm diameter disc that means the entire
filter. The media collecting particulate are filters made of
polycarbonate that do not interfere with the signal. The
results shown hereafter take into account the possible
traces detected in blank analyses.
The soluble organic fraction can also be extracted from
the particulate collected on fiberglass filters in order to
analyze Polycyclic Aromatic Hydrocarbons (PAH). This
soluble fraction is extracted with dichloromethane in hot
and pressurized conditions in an ASE (Accelerated
Solvent Extractor). The PAH are then separated by liquid
chromatography and their concentration is determined by
fluorescence detection.
The mass of sulfates contained in the particulate is
determined using ionic chromatography. The filters are
treated with ammonia to form ammonium sulfate which is
extracted with a water-isopropanol mix. Anions are then
separated through an ion exchange resin, and ionic
chromatography leads to the concentration of the
resulting sulfuric acid.
RESULTS
PARTICULATE SIZE DISTRIBUTION, SMOKE LEVEL
AND PARTICULATE MATTER MASS EMISSION
The general observation determined from the full scope
of the SMPS results show that the heavy-duty engines
emissions are representative of Diesel engines
emissions in general : depending on the engine and test
condition, the particulate are spread out in an
accumulation mode centered around 60 to 120 nm over
the totality of the tests, sometimes coupled to a
nucleation mode centered on a diameter smaller than 30
nm. The maximum concentration of the accumulation
mode reaches about 10
7
particles per cm
3
, while that of
the nucleation mode may reach 10
8
particles per cm
3
as
with the emulsion (Fig. 1). In this case, the nucleation
mode is due to the fuel in itself, providing a fine spray by
the flash ebullition of the emulsified water. Nucleation
mode should not be due to the water provided by the
fuel, since this contribution is far lower than the one of
the water contained in the intake air.
The dilution ratio slightly impacts the particulate
distribution : a lower dilution ratio (5 vs. 15) may induce a
somewhat higher nucleation peak and a little smaller
median diameter, as described in other studies
3,4
.
1.0E+04
1.0E+05
1.0E+06
1.0E+07
1.0E+08
1.0E+09
10 100 1000
Diameter (nm)
d
N
/
d
l
o
g
D
p

(
#
/
c
m
3
)
Water in fuel emulsion - dilution 5
Water in fuel emulsion - dilution 15
Euro2000 Diesel fuel - dilution ratio 5
Euro2000 Diesel fuel - dilution ratio 15
Fig. 1 : B50, Euro II, emulsion and Euro2000 & impact of
dilution ratio
The smoke levels and mass emissions are well linked to
the concentration in particulate larger than 100 nm, i.e.
the heaviest ones, and not to the peak of the nucleation
mode or to the total number of particulate. This trend is
particularly obvious with the Euro II engine considering
both effects of fuel and injection timing (fig. 2, 3 & 4).
Advancing the injection timing results in a larger premix
combustion and thus a smaller diffusion combustion,
inducing a reduction in particulate, smoke and PM
emissions.
1.0E+04
1.0E+05
1.0E+06
1.0E+07
1.0E+08
1.0E+09
10 100 1000
Diameter (nm)
d
N
/
d
l
o
g
D
p

(
#
/
c
m
3
)
0
2.5
5
7.5
10
0
2.5
5
7.5
10
Water in
fuel
emulsion
Euro2000
Diesel fuel
Injection
timing /
static
Fig. 2 : Influence of the injection timing on particulate
concentration and size distribution, B50, Euro II
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0 2.5 5 7.5 10
Injection timing / static
S
m
o
k
e

(
F
S
N
)
Euro2000 Diesel fuel
Water in fuel emulsion
Fig. 3 : Influence of the injection timing on smoke
emission level, B50, Euro II
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0 2.5 5 7.5 10
Injection timing / static
P
M

(
g
/
k
W
.
h
)
Euro2000 Diesel fuel
Water in fuel emulsion
Fig. 4 : Influence of the injection timing on particulate
matter mass emission, B50, Euro II
The settings influence on particulate emission and size
distribution is the same whatever the engine technology.
Advancing the injection timing reduces the number of
particulate, as well as cutting the EGR out, increasing the
injection pressure or activating a post injection. On the
opposite, activating a pilot injection increases the number
of particulate. Usually, the higher the concentration in the
accumulation mode, the larger the median diameter. A
few examples are given in fig. 5 to 7. Note that Euro IV
engine only has EGR and that standard settings for Euro
III engine are composed of a main injection and a post-
injection while the two others only use one single
injection.
Euro II engine - Euro2000 Diesel fuel - C25 - dilution ratio 5
0.0E+00
2.0E+06
4.0E+06
6.0E+06
8.0E+06
1.0E+07
1.2E+07
1.4E+07
1.6E+07
1.8E+07
+10 +7.5 standard +5 +2.5 +0
Inj. timing / static ()
T
o
t
a
l

c
o
n
c
e
n
t
r
a
t
i
o
n

(
c
m
-
3
)
0
10
20
30
40
50
60
70
M
e
d
i
a
n

d
i
a
m
e
t
e
r

(
n
m
)
Total concentration
Median diameter
Fig. 5 : Influence of the injection timing on particulate
concentration and median diameter, C25, Euro II
Euro III engine - Euro2000 Diesel fuel - B50 - dilution ratio 5
0.0E+00
1.0E+06
2.0E+06
3.0E+06
4.0E+06
5.0E+06
EGR 0% inj. pressure
+100b
pilot & post-
injection
standard inj. timing -2 without post-
inj.
T
o
t
a
l

c
o
n
c
e
n
t
r
a
t
i
o
n

(
c
m
-
3
)
0
10
20
30
40
50
60
M
e
d
i
a
n

d
i
a
m
e
t
e
r

(
n
m
)
Total concentration
Median diameter
Fig. 6 : Influence of the injection timing on particulate
concentration and median diameter, B50, Euro III
Euro IV engine - Euro2000 Diesel fuel - B50 - dilution ratio 5
0.0E+00
1.0E+06
2.0E+06
3.0E+06
4.0E+06
5.0E+06
6.0E+06
7.0E+06
8.0E+06
9.0E+06
1.0E+07
inj. pressure
+100 bar
EGR 0% post-injection standard pilot injection Inj. timing -2
T
o
t
a
l

c
o
n
c
e
n
t
r
a
t
i
o
n

(
c
m
-
3
)
0
20
40
60
80
100
120
M
e
d
i
a
n

d
i
a
m
e
t
e
r

(
n
m
)
Total concentration
Median diameter
Fig. 7 : Influence of the injection timing on particulate
concentration and median diameter, B50, Euro IV
The settings influence on the nucleation mode is not
systematic, but note that its occurrence and intensity are
enhanced by the settings producing few particulate in the
accumulation mode, that means when there is less
adsorption matter. Indeed, volatile components need an
adsorption surface onto which condense. Thus it must be
noticed that reducing the particulate mass emitted can
lead to an increase of the number of the smallest
particulate, as it is shown in fig. 8 to 10.
1.0E+04
1.0E+05
1.0E+06
1.0E+07
1.0E+08
1.0E+09
10 100 1000
Diameter (nm)
d
N
/
d
lo
g
D
p

(
#
/
c
m
3
)
0
2.5
5
7.5
10
0
2.5
5
7.5
10
Water in
fuel
emulsion
Euro2000
Diesel fuel
Injection
timing /
static
Fig. 8 : Impact of fuel and injection timing on particulate
concentration and size distribution, C25, Euro II
0.0E+00
4.0E+06
8.0E+06
1.2E+07
1.6E+07
2.0E+07
2.4E+07
2.8E+07
3.2E+07
10 100 1000
Diameter (nm)
d
N
/
d
l
o
g
D
p

(
#
/
c
m
3
)
without post-injection
inj. timing -2
standard
with pilot-injection
EGR 0%
inj. pressure +100b
Euro 2000
Diesel fuel
Fig. 9 : Influence of engine settings on particulate
concentration and size distribution, C25, Euro III
Suppressing the EGR increases the oxygen content of
the air/fuel mix and thus the oxidation rate. Increasing
the injection pressure leads to a better atomization of fuel
and to a shorter injection duration. A post-injection re
oxidize the particulate first produced.
0.0E+00
5.0E+06
1.0E+07
1.5E+07
2.0E+07
2.5E+07
10 100 1000
Diameter (nm)
d
N
/
d
l
o
g
D
p

(
#
/
c
m
3
)
inj. timing -2
pilot-injection
standard
post-injection
inj. pressure +100 bar
EGR 0%
Euro
2000
Diesel
fuel
Fig. 10 : Influence of engine settings on particulate
concentration and size distribution, C25, Euro IV
The particulate emitted using the City Fuel (on Euro III
and IV engines) are spread out similarly as when
Euro2000 fuel is used, even though the number is
higher. However, there are less large particulate with this
fuel, resulting in a lower mass collected. Number and
volume of particulate are reported on fig. 11 and must be
linked to the indicated mass collected on filters.
0.0E+00
2.0E+06
4.0E+06
6.0E+06
8.0E+06
1.0E+07
1.2E+07
1.4E+07
1.6E+07
1.8E+07
10 100 1000
Diameter (nm)
d
N
/
d
l
o
g
D
p

(
#
/
c
m
3
)
0.0E+00
5.0E+12
1.0E+13
1.5E+13
2.0E+13
2.5E+13
d
V
/
d
l
o
g
D
p

(
n
m
3
/
c
m
3
)
Euro2000 - PM : 0.21 g/kW.h
City fuel - PM : 0.07 g/kW.h
Fig. 11 : Estimation of particulate volume, i.e. mass,
from SMPS data, C25, Euro IV
Water-in-fuel emulsion, tested with Euro II engine, leads
to very different results : concentration in large diameter
particulate is reduced while nucleation mode peak is ten
times higher. The flash ebullition of water droplets leads
to a fine atomization of the fuel. Tests performed with the
Euro2000 Diesel fuel and water injected at the inlet do
not lead to the same results at all (Fig. 12). This confirms
the importance of fuel nature on particulate creation.
1.0E+04
1.0E+05
1.0E+06
1.0E+07
1.0E+08
10 100 1000
Diameter (nm)
d
N
/
d
lo
g
D
p

(
#
/
c
m
3
)
Euro2000 Diesel fuel
Aquazole
Euro2000 Diesel fuel + 15% water
Fig. 12 : Impact of water, emulsified in fuel or port
injected, on particulate size distribution, B50, Euro II
PARTICULATE COMPOSITION ACCORDING TO
THEIR SIZE
MINERAL ELEMENTS
To be accurately analyzed by PIXE technique, particulate
have to be collected on filters made of polycarbonate
which are not as rough as fiberglass filter. Particulate
bouncing to inferior impaction plates explains the slipping
of the particulate size distribution to the smaller
diameters. The comparison of the results obtained with
both polycarbonate and fiberglass filters is shown in
figure 13. Note that a very low mass is required to
perform such analysis. Therefore the sampling duration
is reduced from 3 hours for sulfate and PAH analyses to
10 minutes. Nevertheless, a mass higher than 0.1 mg is
necessary to calculate reliable concentrations.
Euro III engine - Euro2000 Diesel fuel - B50
0
5
10
15
20
25
0.032 -
0.064
0.064 -
0.110
0.110 -
0.179
0.179 -
0.275
0.275 -
0.421
0.421 -
0.680
0.680 -
1.05
1.05 -
1.71
1.71 -
2.60
2.60 -
4.21
4.21 -
7.03
7.03 -
10.8
> 10.8
Diameter range (m)
M
a
s
s

r
e
p
a
r
t
i
t
i
o
n

(
%
)
Polycarbonate
Glassfiber
Polycarbonate filter : particulate slip to lower impaction plates
Fig. 13 : Influence of impaction filter type on particulate
mass distribution sampled by LPI, B50, Euro III
Mineral elements concentrations determined by PIXE
technique show slightly different results considering each
engine, however species originating from both fuel and
lubrication oil as well as from engine wear are always
spread out through two modes, while those coming from
engine wear only form one single mode, centered
between 1 and 5 m. The former elements are sulfur,
mainly originating from fuel but also from lube oil,
calcium (detergent and antioxidant additives), zinc,
phosphorous (anti-wear and antioxidant additives) and
potassium present in lube oil (fig. 14); the latter are iron,
chrome, manganese, molybdenum, nickel, bromine and
lead, all originating mainly from piston rings, cylinder
liners, valves and bearings (fig. 15). Molybdenum may
also be found in anti-wear additives what could explain
the second mode observed in fig. 15, but it is not found in
the oil analysis. Origin of copper and chloride is not clear
as they are not detected in oil analysis, but chloride may
come from air. Less metallic elements come from engine
wear than from lube oil and fuel. The mode is centered
between 1 and 5 m, mainly 2 m. The presence of
particles larger than 5 m in servicing oil analysis would
indicate an abnormal wear, what is not the case for any
of the three engines. The results showed on fig. 13 to 15
are those of Euro III engine. The results of the 4 to 7 m
impaction plate is removed due to an insufficient
collected mass.
0
2
4
6
8
10
12
14
0.032 -
0.064
0.064 -
0.110
0.110 -
0.179
0.179 -
0.275
0.275 -
0.421
0.421 -
0.680
0.680 -
1.05
1.05 -
1.71
1.71 -
2.60
2.60 -
4.21
4.21 -
7.03
7.03 -
10.8
> 10.8
Diameter range (m)
S
u
l
f
u
r

c
o
n
c
e
n
t
r
a
t
i
o
n

(
%
)
0
1
2
3
4
5
6
7
O
t
h
e
r

e
l
e
m
e
n
t
s

c
o
n
c
e
n
t
r
a
t
i
o
n

(
%
)
S
Ca
Zn
P
Fig. 14 : Distribution of elements originating mainly from
lubrication oil, B50, Euro III
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
0.032 -
0.064
0.064 -
0.110
0.110 -
0.179
0.179 -
0.275
0.275 -
0.421
0.421 -
0.680
0.680 -
1.05
1.05 -
1.71
1.71 -
2.60
2.60 -
4.21
4.21 -
7.03
7.03 -
10.8
> 10.8
Diameter range (m)
I
r
o
n

c
o
n
c
e
n
t
r
a
t
i
o
n

(
%
)
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
0.22
O
t
h
e
r

m
e
t
a
l
s

c
o
n
c
e
n
t
r
a
t
i
o
n

(
%
)
Fe
Cr
Mn
Mo
Pb
Ni
Fig. 15 : Distribution of elements originating mainly from
engine wear, B50, Euro III
SULFATE CONCENTRATION
Using the Euro2000 Diesel fuel, the mass of sulfates is
about 2 to 3 % of the accumulation mode particulate,
with no dependence on the particulate size (Fig. 16).
With the Euro III engine, for which a nucleation mode is
identified by SMPS, sulfate concentration in the smallest
particulate reach almost 20%. The sulfate concentration
in the particulate is higher over the entire diameter range
with this engine, what must be due to the less particulate
mass emission despite quite a same fuel consumption.
0
2
4
6
8
10
12
14
16
18
20
0.032 -
0.064
0.064 -
0.110
0.110 -
0.179
0.179 -
0.275
0.275 -
0.421
0.421 -
0.680
0.680 -
1.05
1.05 -
1.71
1.71 -
2.60
2.60 -
4.21
4.21 -
7.03
7.03 -
10.8
> 10.8
Diameter range (m)
S
u
l
f
a
t
e

c
o
n
c
e
n
t
r
a
t
i
o
n

i
n

p
a
r
t
i
c
u
l
a
t
e

(
%
)
Euro II (B50-PM: 0.08 g/kW.h)
Euro III (B50-PM: 0.05 g/kW.h)
Euro IV (B50-PM: 0.15 g/kW.h)
Fig. 16 : Distribution of sulfates contained in particulate,
B50
PAH ANALYSIS
Two C
16
H
10
PAH are mainly present in the particulate
emitted by the three engines, fluoranthene and pyrene,
representing 20 to 140 ppm of particulate mass. C
18
H
12
Chrysene and benzo(a)anthracene are also present in
concentration reaching 10 to 30 ppm, but not for all
engines. The concentration of other PAH is less than 10
ppm. No correlation can be found with the size for Euro II
engine, while the trends observed for Euro III and IV
engines are totally different (Fig. 17, 18 & 19). The
concentration does not appear to be linked to the size of
the particulate in any consistent way considering all
engines.
As they are precursors of Diesel particulate, PAH are
found in particulate at every range of size. It is often
stated that nuclei mode particulate have a higher density
than accumulation mode particulate. This should not be
attributed to the PAH content but to their lower porosity.
0
10
20
30
40
50
60
70
80
0.032 -
0.064
0.064 -
0.110
0.110 -
0.179
0.179 -
0.275
0.275 -
0.421
0.421 -
0.680
0.680 -
1.05
1.05 -
1.71
1.71 -
2.60
2.60 -
4.21
4.21 -
7.03
7.03 -
10.8
> 10.8
Diameter range (m)
C
o
n
c
e
n
t
r
a
t
i
o
n

i
n

t
h
e

p
a
r
t
i
c
u
l
a
t
e

(
p
p
m
)
Fluoranthene
Pyrene
Chrysene
B(a)Anthracene
Fig. 17 : Main PAH distribution, B50, Euro II
0
20
40
60
80
100
120
140
160
0.032 -
0.064
0.064 -
0.110
0.110 -
0.179
0.179 -
0.275
0.275 -
0.421
0.421 -
0.680
0.680 -
1.05
1.05 -
1.71
1.71 -
2.60
2.60 -
4.21
4.21 -
7.03
7.03 -
10.8
> 10.8
Diameter range (m)
C
o
n
c
e
n
t
r
a
t
i
o
n

i
n

t
h
e

p
a
r
t
i
c
u
l
a
t
e

(
p
p
m
)Fluoranthene
Pyrene
Chrysene
Fig. 18 : Main PAH distribution B50, Euro III
0
5
10
15
20
25
30
35
40
45
50
0.032 -
0.064
0.064 -
0.110
0.110 -
0.179
0.179 -
0.275
0.275 -
0.421
0.421 -
0.680
0.680 -
1.05
1.05 -
1.71
1.71 -
2.60
2.60 -
4.21
4.21 -
7.03
7.03 -
10.8
> 10.8
Diameter range (m)
C
o
n
c
e
n
t
r
a
t
i
o
n

i
n

t
h
e

p
a
t
i
c
u
l
a
t
e

(
p
p
m
)Fluoranthene
Pyrne
Fig. 19 : Main PAH distribution B50, Euro IV
CONCLUSION
The aim of the Primequal study is to characterize the
particulate emissions of the different engine technologies
equipping the current vehicle fleet with the adapted fuels.
The most recent engine is also tested with the kind of
fuel that will be used in 2005. Three Renault VI engines
were tested, one Euro II MIDR 62045, a Euro III DCI6
and a Euro IV like single cylinder prototype engine. The
main results are as follows :
Particulate diameter distribution is made of a so-
called accumulation mode whose maximum
concentration is about 10
7
particulate per cm
3
,
centered around 60 120 nm, in some cases
coupled to a nucleation mode centered on a
diameter smaller than 30 nm.
Smoke level and particulate mass emission are well
linked to accumulation mode intensity and especially
to the concentration in particulate with a diameter
bigger than 200 nm.
Nucleation mode is more likely to occur with engine
settings producing few accumulation particulate, that
is to say when there is less adsorbent matter.
Particulate emissions when using either the class 1
City Fuel or the standard Euro 2000 Fuel exhibit
basically a similar size distribution pattern. However,
although leading to higher concentrations in the
smaller size range (< 120 nm ), the class 1 City fuel
allows for a significantly reduced production of larger
particulate. Thus, the overall mass is lowered.
Water-in-fuel emulsion reduces the amount of big
particulate but induces a high nucleation peak (10
8
particulate per cm
3
). The impact of water minerals
have to be checked (an IFP/ADEME program on this
topic is about to be achieved).
Mineral elements originating from fuel and lube oil as
well as from engine wear are distributed in a bi-
modal way, while those originating from engine wear
only are distributed in one single mode centered
between 1 and 5 m.
Sulfates represent 2 to 3 % of accumulation mode
particulate mass, and up to 20 % nucleation mode
particulate mass.
Fluoranthene and pyrene are the two mainly emitted
PAH by all engines. Their concentration is not linked
to the particulate size.
To conclude, fuel composition and engine settings
strongly impact the quantity of particulate and their
distribution regarding their size, whatever the engine
technology. Particulate composition in mineral elements
is however weakly bound to the size.
ACKNOWLEDGMENTS
This program was sponsored by ADEME (French
Agency for Environment and Energy Management), PSA
Peugeot-Citron, Renault, Renault VI and IFP. We thank
Loys Pierron at Renault VI Powertrain for supplying the
engines and for the technical support.
REFERENCES
1. K. Donaldson, X. Y. Li, W. MacNee, J. Aerosol
Science, 1998, 29, 553-560
2. G. Oberdrster, 1998, "Health effects of ultrafine
particles experimental studies,
Gesundheitsgefrdung durch Feinstube am
Arbeitsplatz, Quantifizierung mechanischer
Belastungen, Arbeitsmedizin in der EU, ed.
Baumgartner, sterreichische Gesellschaft fr
Arbeitsmedizin
3. I. Abdul-Khalek, D. Kittelson, F. Brear, "The
Influence of Dilution Conditions on Diesel Exhaust
Particle Size Distribution Measurements, SAE 1999-
01-1142
4. M. Lapuerta, O. Armas, R. Ballesteros, A. Duran,
"Influence of Mini-tunnel Operating Parameters and
Ambient Conditions on Diesel Particulate
Measurement and Analysis", SAE 1999-01-3531