Fuel 118 (2014) 130136

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Inuence of butanoldiesel blends on particulate emissions of

a non-road diesel engine
Zhi-Hui Zhang, Rajasekhar Balasubramanian
Department of Civil and Environmental Engineering, Faculty of Engineering, National University of Singapore, 1 Engineering Drive 2, E1A 02-19, Singapore 117576, Singapore

h i g h l i g h t s
 Butanol addition to diesel in blends inuences particulate emissions.
 It reduces PM2.5 and elemental carbon emissions while increases the proportion of organic carbon in particles.
 The total number concentrations of volatile and non-volatile particles decreases signicantly.
 The higher proportion of butanol in blends leads to higher particle-phase PAHs emissions.
 The cytotoxicity of particle extracts from diesel and blended fuels shows no signicant difference.

a r t i c l e

i n f o

Article history:
Received 14 July 2013
Received in revised form 12 October 2013
Accepted 27 October 2013
Available online 7 November 2013
Keywords:
Diesel particles
Butanol
Polycyclic aromatic hydrocarbons
Cell cytotoxicity

a b s t r a c t
Ultralow sulfur diesel (ULSD) fuel was blended with 5%, 10%, 15% and 20% of butanol by volume. The
effects of these blended fuels on physicochemical characteristics of particulate emissions and the cytotoxicity of particulate extracts from a single cylinder, direct injection stationary diesel engine were investigated with the engine working at a constant speed of 3000 revolutions per min (rpm) and at 25%, 50%
and 75% of its maximum output power. The results indicated a decrease in particulate mass and elemental carbon (EC) emissions, while an increase in the proportion of organic carbon (OC) in the particles with
an increase in butanol in the fuel. Compared to the ULSD, the total number concentrations of volatile and
non-volatile particles were reduced signicantly for blended fuels, whereas the number of particles with
diameter less than 15 nm increased for 15% and 20% butanol blends at low engine load. The increased
total polycyclic aromatic hydrocarbons (PAHs) emissions, as well as their carcinogenic potency was also
observed when the blends contained 15% and 20% butanol. In general, all the particle extracts showed a
decline in cell viability with their increased dose and with the increased engine load while maintaining
the same dose, based on the MTT assay.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Diesel engines are widely used in both mobile and stationary
applications due to their reliability, durability and high fuel efciency. However, high emissions of airborne particulate matter
(PM) from diesel engines represent a major contributor to urban
carbonaceous aerosols, which are suspected to have an adverse impact on local air quality as well as global climate change and also
known to cause adverse health effects [1,2]. The development of
alternative fuels such as alcohols and biodiesel to partly or totally
replace petroleum diesel and thus to reduce PM emissions is getting a high priority as a result of increased public concern about
energy security and environmental pollution [3].
Butanol has recently drawn considerable research attention as
an alternative fuel for diesel engines due to its unique properties.
Corresponding author. Tel.: +65 65165135; fax: +65 67744202.
E-mail address: ceerbala@nus.edu.sg (R. Balasubramanian).
0016-2361/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.10.059

For example, butanol has higher heating value and cetane number,
more miscibility with diesel, and less volatility compared to methanol and ethanol [4]. In addition, butanol contains more oxygen
content than biodiesel, which can further reduce the soot emissions. Furthermore, the viscosity of butanol is also more suitable
for diesel engines compared to biodiesel [4]. As these properties
are close to those of petroleum diesel, butanol is becoming a more
attractive fuel than low-chain alcohols and biodiesel [4]. Several
studies have been carried out on the use of butanoldiesel blends
in diesel engine and its effects on engine performance and exhaust
emissions were investigated [510]. These studies revealed the
benecial effects of using various blends of butanol with diesel fuel
on smoke and PM emissions, but at the expense of higher hydrocarbon (HC) emissions.
The effects of butanoldiesel blends on particle number size
distributions and particle chemical characteristics remain poorly
understood. In previous tests, the butanoldiesel blends showed
reduction in smoke opacity or PM emissions, caused by a reduction

Z.-H. Zhang, R. Balasubramanian / Fuel 118 (2014) 130136

in large particles, while there might be an increase in sub-micron

sized particles. Thus, the increased emission of the sub-micron particles and the reduced emission of larger size particles would
change the ambient air particle size distribution as well as the
characteristics of the inhalation exposure [11]. Moreover, it is
known that the application of oxygenated fuel in diesel engines
might change the fraction of EC and OC in particles. The EC suspended in the atmosphere can effectively absorb solar radiation,
thus affecting the energy redistribution and global climate [2],
while some semi-volatile hydrocarbons including polycyclic aromatic hydrocarbons (PAHs) in the OC fraction are suspected human
carcinogens [12]. In view of these concerns, there is a need to systematically investigate changes in the particulate size distributions
and their corresponding number concentrations, particulate chemical composition when butanol is blended with diesel and used in
engines.
Previous studies on the inuence of butanoldiesel blends on
PM emissions were mainly conducted on the on-road diesel
engines. However, there is paucity of data in the literature for
evaluating the fuel use and PM emissions from non-road diesel
construction equipment [10]. Although non-road diesel engines
contribute a small fraction of the total number of diesel engines
in operation, they account for a disproportionate fraction of the
PM and NOx emissions because they typically have minimal emissions control [12]. While it does not represent advanced high-pressure common rail injection technologies increasingly used in new
engine designs, it can represent an important set of legacy engine
technologies likely to remain in use for decades. To ll this knowledge gap, the present study was initiated with the goal of assessing
the potential impact of butanoldiesel blends on the physical,
chemical and toxicological properties of PM emitted by a non-road
diesel engine under different load conditions. Results from these
tests may offer better insight on the effect of butanol on diesel particulate emissions, and may prove to be useful for controlling and
regulating PM emissions from non-road diesel engines.
2. Experimental section
2.1. Test engine and fuels
The schematic of the experimental system is shown in Supplementary Fig. S1. Experiments were carried out on a single cylinder,
four-stroke, direct-injection, diesel engine (L70AE, Yanmar Corporation) connected to a 4.5 kW generator. The generator is connected with several resistance heaters, and the engine load is
adjusted by the variation of the total resistance. The diesel engine
has a capacity of 296 cm3 with bore and stroke of 78 mm  62 mm,
a xed speed of 3000 rpm. The detailed engine specications are
shown in Supplementary Table S1. Other similar small diesel engine have been used in [5,9] for investigating the inuence of butanoldiesel blends on engine emissions. The fuels used include
ULSD with less than 50-ppm (parts per million) by weight of sulfur
and anhydrous n-butanol 99.8% purity (SigmaAldrich). Major
properties of the test fuels are shown in Supplementary Table S2.
The blended fuels contained 5%, 10%, 15% and 20% by volume of
butanol, and are identied as Bu5, Bu10, Bu15 and Bu20 fuels.
2.2. Particulate sampling and testing
All the particulate sampling and measuring instruments used in
this study are listed with their specic characteristics in Supplementary Table S3. A two-stage Dekati mini-diluter (DI-2000, Dekati Ltd.) was used for diluting the exhaust gas for sampling. The
diluter provides primary dilution in the range of 8:1 to 6:1,
depending on the engine operating conditions, while the secondary

131

dilution system provides a further dilution of 8:1. The actual dilution ratio was evaluated based on measured CO2 concentrations in
the raw exhaust, in the background air and in the diluted exhaust.
The CO2 concentration was measured with a non-dispersive infrared analyzer (MRU Vario Plus, Germany, 0.5% accuracy). This measurement was done for every test, and all data presented in this
article have been dilution-corrected to represent engine-out
conditions.
The rst stage diluter was only used to cool the sampling gas
temperature below 52 C for particulate sampling. PM with aerodynamic diameter 62.5 lm (PM2.5) was collected on pre-combusted (650 C for 12 h) 47 mm quartz ber lters (Whatman,
USA) by using two Mini-Vol low volume particulate samplers
(Air metrics Ltd.; 5 L min 1 ow rate). Before and after sampling,
the lters were allowed to equilibrate in a humidity-controlled
chamber at constant temperature and humidity (22 3 C,
35 8% RH), and weighed using a microbalance (Sartorius MC5,
accuracy of 1 lg) for quantifying total PM2.5 mass emissions. After
being weighed, the lters were kept in glass petri dishes and stored
under refrigeration at 20 C for the subsequent analysis of PAHs
contents and toxicology. A thermal/optical carbon aerosol analyzer
(Sunset Labs, Forest Grove, Oregon, USA) was use to quantify EC
and OC emissions according to the NIOSH 5040 reference method
[13].
The number concentration and size distribution of volatile and
non-volatile particles in the secondary dilution stage were measured by a Fast Mobility Particle Sizer (FMPS, Model 3091, TSI
Incorporated, USA) for particles in the size range of 5.6560 nm.
In this setup, two diluters were used in series, with the rst stage
being heated to 190 C in order to minimize thermophoretic deposition. During the non-volatile particle number emission experiments, a thermodenuder (TD, Dekati Ltd.) was placed in-line
between the secondary stage diluter and the FMPS. In the TD, the
volatile and semi-volatile compounds of the particles are vaporized
by heating the sample aerosol, and then are gradually cooled and
adsorbed into active charcoal so that they do not re-condense onto
the remaining solid particles. The TD diffusion losses were estimated using the method in [14], and the diffusion loss-corrected
particle size distributions are presented in this article.

2.3. Particle-phase PAHs

Particle-phase PAHs were extracted from the quartz lter samples in 50/50 hexane/acetone (HPLC-grade, Fisher Scientic) mixture using a closed vessel microwave-assisted extraction system
(MLS-1200 mega, Mileston, Italy) in accordance with the US EPA
method 3546 [15]. Each of the eluents was divided into two equal
parts, with one part for subsequent PAHs analysis, and the other
part for toxicological analysis. More details of this method including the chemical analysis of 16 US priority PAHs by gas chromatography/mass spectrometry (Shimadzu GC-MS-QP 2010, Japan) have
been discussed in our previous publication [16].
The 16 EPA PAHs are separated into three different molecular
weight ranges: Low molecular weight (LMW) PAHs are two and
three rings PAHs including naphthalene (Nap), acenaphthylene
(AcPy), acenaphthene (AcP), uorine (Flu), phenanthrene (PA)
and anthracene (Ant). Middle molecular weight (MMW) PAHs are
four rings PAHs including uoranthene (FL), pyrene (Pyr),
benzo[a]anthracene (BaA) and chrysene (CHR). High molecular
weight (HMW) PAHs are ve and six rings PAHs including
benzo[b]uoranthene (BbF), benzo[k]uoranthene (BkF), benzo[a]pyrene (BaP), dibenzo[a,h] anthracene (DBA), indeno[1,2,3,-cd]pyrene (IND) and benzo[ghi] perylene (BghiP). The total-PAH data
represented the sum of the 16 individual PAHs. The overall toxicity
was dened as the sum of Benzo[a]pyrene equivalent (total BaPeq),

Z.-H. Zhang, R. Balasubramanian / Fuel 118 (2014) 130136

which was each PAH concentration multiplied by its toxicity

equivalent factor (TEF) as recommended by Nisbet and LaGoy [17].

3.1. PM2.5 and carbon emissions

PM2.5 has been classied into three portions for this study: EC,
OC and non-carbonaceous materials (such as sulfates, nitrates,
metals and ash). The variation of their concentrations and the
EC/OC ratios is shown in Fig. 1. In general, both EC and OC, and thus
the PM2.5 concentrations increased with the engine load for each
fuel. Moreover, the increase in EC concentrations with engine load
was higher than that of OC concentrations. These results are consistent with those reported by Liu et al. [12] and Shi et al. [19].
The butanoldiesel blends showed no signicant change in the
PM2.5 concentrations at low engine load. However, at medium and
high engine loads, the reduction of PM2.5 concentrations became
signicant when the blended fuels contained more proportion of
butanol. The PM2.5 concentrations were reduced by 4.318.7%
and 6.925.0%, corresponding to medium and high engine loads
under different proportion of butanol in blended fuels. Compared
to ULSD, the blends also resulted in 12.222.7%, 31.141.6%,

75% engine load

Non-carbonaceous
materials
EC
OC

1.0
0.8
0.6

EC/OC

0.4

60

0.2
40
0.0
20

-0.2

-0.4

Bu20
Bu15
Bu10
Bu5
ULSD

Combustion experiments were performed at a constant engine

speed of 3000 rpm and at three engine loads, corresponding to
25%, 50% and 75% maximum engine power output, respectively.
For particulate sampling and analysis, three tests were carried
out for each operating condition and the results were found to
agree with each other at 95% condence level. For determining particle number concentrations and size distributions, ve measurements were taken at each mode of operation and the average
values are presented. The experimental standard errors in the measurements have been determined based on the method of Kline
and McClintock [18]. The standard errors were 3.7%, 3.5%, 5.8%
and 2.6%, for PM2.5 mass, EC, OC concentrations and particle number concentrations, respectively. Results obtained from different
fuels were compared using the two-sided Students t-test to examine if they are signicantly different from each other at 95% condence level.

50% engine load

Bu20
Bu15
Bu10
Bu5
ULSD

3. Results and discussion

80

25% engine load

Bu20
Bu15
Bu10
Bu5
ULSD

The residue from the particle extracts was re-suspended in

DMSO (Dimethyl sulfoxide, Bioreagents, SigmaAldrich) and subsequently in cell exposure medium. The nal concentration of
DMSO in the medium did not exceed 0.5% (v/v). The human-type
II cell alveolar epithelial cell line A549 (American Type Culture Collection) was cultured in DMEM (Dulbeccos Modied Eagle Medium, Gibco) with 10% FBS (fetal bovine serum) at 37 C in 5%
CO2. A549 cells were seeded into 96-well plates at a concentration
of 1  105 cells/mL, and cultured for 24 h to allow adherence and
proliferation. After this period, the medium was replaced, and
the cells were exposed to particle extracts contained in DMEM
for another 24 h. At the end of the treatments, MTT (3-(4,5Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide, a yellow
tetrazole, SigmaAldrich) (0.5 mg/mL nal concentration) was
added to the wells and incubated for 4 h. The medium was removed, and 100 lL DMSO was added to dissolve the blue formazan
crystals. The absorbance value of the MTT formazan in each well
was measured using an Innite 200 PRO microplate reader (Tecan
Group Ltd, Germany) at a wavelength of 570 nm. Each sample was
tested in six replicate wells, and the data on cell viability are reported as relative decrease compared to the control, considered
as 100% of viable cells.

100
3
Concentration (mg/m )

2.4. Cytotoxicity of particle extracts

120

EC/OC

132

Test Fuel
Fig. 1. Effect of butanoldiesel blends on PM2.5, EC and OC concentrations, and EC/
OC ratios.

38.451.7% and 46.060.6% EC emissions reduction for Bu5,

Bu10, Bu15 and Bu20, respectively, depending on the engine loads.
The OC emissions remained almost unchanged, and consequently,
the decrease of PM2.5 emissions due to blended fuels can be attributed predominantly to the EC emission reduction. This is reected
also in the EC/OC ratios given in Fig. 1, which ranged for the ULSD
from 0.18 to 0.94 as compared to the values between 0.09 and 0.56
for the Bu20. Previous studies by Yao et al. [6], Rakopoulos et al.
[7,8], Dogan [9] and Lin et al. [10] also reported a signicant reduction in smoke or particulate mass emissions when the engine was
operated on butanoldiesel fuel blends. The results from their
studies together with those from this investigation reveal that
butanol addition to diesel is effective at reducing PM emissions,
especially at high engine load with high proportion of butanol in
blended fuels.
Diesel particulate emissions are composed predominantly of
EC and OC. The EC stems from fuel droplet pyrolysis in the
fuel-rich zone under high pressure and temperature [20,21],
while the OC originates from unburned fuel, lubricating oil, and
combustion byproducts [20,22]. Therefore, the increase in both
EC and OC concentrations with engine load is consistent with
the higher fuel usage, lower air/fuel ratio, and higher pressure
and temperature at higher loads [20,21]. With butanol addition,
on one hand, the oxygen in the fuel could be effectively delivered
to the pyrolysis zone of the burning diesel spray to suppress soot
formation, leading to reduction in EC emission. On the other
hand, as pointed out in previous studies in the literature [6,8],
the diesel fuel blended with butanol tends to enhance the fuel
air mixing process and gave more premixed combustion, leading
to a reduction in soot emissions. The lower EC or soot emissions
led to lower PM2.5 mass concentrations. The results from this
investigation also reveal that butanol is more benecial in reducing PM2.5 concentrations at the high engine load. Two factors are
likely to contribute to this observation. Firstly, less fuel is injected
at low engine load and therefore less fuel is burned during the
mixing-controlled phase of combustion. Since soot formation occurs primarily during this mixing-controlled phase, the effect of
the oxygenated fuel on PM and EC reduction would be less pronounced at low engine load. Secondly, at low load, the air/fuel ratio is high, thus the role played by the oxygenates in providing
extra oxygen to support diesel fuel combustion is less important,
compared with the high load case.

Z.-H. Zhang, R. Balasubramanian / Fuel 118 (2014) 130136

3.2. volatile and non-volatile particle number concentrations and size

distribution
In this study, a thermal denuder (TD) was used to removal
semi-volatile particles. Both the volatile and non-volatile total particle number concentration and size distributions varied with the
engine load and the butanol content in blends as shown in
Figs. 2ac, while the total particle number concentrations and
the volatile particle geometric mean diameter (GMD) are shown
in Table 1.

dN/dlog(Dp)(particles cm-3) [107]

Volatile

25% engine load

ULSD
Bu5
Bu10
Bu15
Bu20

2
Non-volatile

0
10

100

10

100

Diameter Dp(nm)

dN/dlog(Dp)(particles cm-3) [107]

Volatile

50% engine load

ULSD
Bu5
Bu10
Bu15
Bu20

6
Non-volatile

dN/dlog(Dp)(particles cm-3) [107]

0
10

100

10

100

Diameter Dp(nm)

(C)

18

18
Volatile

15
12

ULSD
Bu5
Bu10
Bu15
Bu20

75% engine load

15
Non-volatile
12

dN/dlog(Dp)(particles cm-3) [107]

(b)

dN/dlog(Dp)(particles cm-3) [107]

dN/dlog(Dp)(particles cm-3) [107]

(a)

0
10

100

10

100

Diameter Dp(nm)
Fig. 2. Effect of butanoldiesel blends on volatile (without TD) and non-volatile
(with TD) particle size distributions.

133

The results from Fig. 2ac show that sizes of particle emissions
are mostly below 100 nm. At low engine load, both volatile and
non-volatile particle size distributions were bimodal, showing
clearly a distinctive nucleation mode with the peak diameters of
810 nm, and an accumulation mode with the peak diameters of
4552 nm, respectively. When the engine load was increased, the
relative intensity of the nucleation mode decreased while that of
the accumulation mode increased, resulting in a shift of the particle size distribution from bimodal mode to single mode. Furthermore, with an increase in engine load, regardless of the fuel
used, the size distribution curves shift upwards and towards larger
size, which may be responsible for an increase in total particle
number concentration and GMD, as shown in Table 1. Characteristics of the size distributions and their dependence on operating
conditions of the engine observed in this study are consistent with
those previously reported in [2224]. It is possible that the presence of the large carbonaceous accumulation mode associated with
higher engine loads provided a large surface area for adsorption of
the volatile material that comprised the nucleation mode, and
therefore suppressed the formation of the nucleation mode [25].
At low engine load, the concentration of the accumulation mode
was lower, so there was less carbonaceous material to suppress
nucleation mode, and consequently, a distinct nucleation mode
was observed.
The variation of particle number concentrations and size distributions caused by blended fuels seems to be associated with the
proportion of butanol in blends and engine load. In general, both
the volatile and non-volatile particle size distribution proles became atter and there was a slight shift of the particles towards
smaller size with an increase in butanol in the blends, indicating
a decrease of particle number concentration. However, the blends
caused an obvious change in volatile and non-volatile nucleation
mode particles at low engine load. Compared to ULSD, Bu5 and
Bu10 led to a reduction of volatile nucleation particles, and showed
no signicant change in the non-volatile nucleation particles. However, the number of volatile and non-volatile particles below
15 nm emitted from Bu15 and Bu20 was obviously increased. At
medium and high engine loads, both the volatile and non-volatile
particles of less than 20 nm from all the fuels were quite low.
Blends showed no signicant change in these particle emissions.
However, the results shown in Table 1 suggested a signicant
reduction in the total number concentration of volatile and nonvolatile particles after adding butanol in the diesel fuel. Compared
to ULSD, from low to high engine load, the total number concentration of volatile particles was reduced by 18.230.2%, 11.645.6%,
and 12.837.9%, respectively, while the corresponding reduction
of non-volatile particles was 16.727.6%, 10.544.3%, and 15.5
40.7%. According to the data shown in Table 1, in general there
was a decrease in GMD for blends as compared to the ULSD, and
these differences reached the level of statistical signicance for
Bu15 and Bu20. The decreased GMD, together with the enhanced
emission of those particles below 15 nm, for Bu15 and Bu20 may
change the diesel particle dynamics in ambient air and should be
carefully considered.
The reduced carbon contents coupled with an increase in oxygen content in the blends may contribute to the reduction of soot
emission in terms of its number concentration and hence total particle number concentration. The reduction in particle number concentration may also reduce the coagulation and agglomeration of
the particles, leading to a reduction in the GMD [26]. However,
the cause for the change in the nucleation mode emission is not
clear and further investigations are needed. The non-volatile core
particles with diameter of 810 nm have been found at idle or
low load conditions, both with light duty and heavy-duty engines
[22,25,27,28]. At low loads, the non-volatile core particles have
been suggested to be formed from fuel aliphatic hydrocarbons

134

Z.-H. Zhang, R. Balasubramanian / Fuel 118 (2014) 130136

Table 1
Total number concentration and geometric mean diameter (GMD) of airborne particles.
Engine load
Volatile particles
25%
50%
75%

(particles cm
GMD (nm)
(particles cm
GMD (nm)
(particles cm
GMD (nm)

Non-volatile particles
25%
(particles cm
50%
(particles cm
75%
(particles cm

) [107]

) [10 ]

) [107]

) [107]
) [107]
3
) [107]
3

ULSD

Bu5

Bu10

Bu15

Bu20

17.6 0.9
35.1 1.1
33.7 1.6
57.6 1.3
69.0 3.4
73.7 1.2

14.4 0.8
34.5 1.0
29.8 1.5
55.2 1.4
60.2 3.2
70.9 2.0

14.0 0.8
31.6 0.9
26.3 1.3
52.9 1.2
55.4 2.8
69.3 1.3

13.4 0.7
28.3 1.1
22.9 1.2
50.7 1.6
50.1 2.5
67.6 1.4

12.3 0.8
23.3 1.3
18.3 1.0
48.8 1.2
42.9 2.2
64.3 1.2

11.8 0.6
23.2 1.1
48.7 2.4

9.8 0.5
20.7 1.1
43.3 2.1

9.2 0.5
17.5 0.9
38.1 1.9

8.7 0.4
16.0 0.7
35.1 1.8

8.5 0. 5
12.9 0.7
30.4 1.5

[28], and the nucleation mode particles were associated with the
growth of the core in the dilution system [27]. At low engine load,
the enhanced hydrocarbon emissions from the higher proportion
of butanol in blends have been reported in the literature [5,79],
which are probably associated with the higher non-volatile core
particle emissions. The higher core emissions combined with the
higher hydrocarbon concentration in the exhaust from Bu15 and
Bu20 seem to have accumulated the formation of more nucleation
mode particles during dilution processes. Schneider et al. [29] suggested that the soluble organic fraction (SOF) in the particles may
pass from the gas phase to the particle phase by two paths: nucleation to form new particles or adsorption onto or absorption into
existing particles. In this investigation, a signicant reduction in
total particle number emission by passing through TD suggested
that the formation of some purely volatile particles in the dilution
and cooling process should be considered as a contributor to increase total particle number emissions, for both ULSD and blended
fuels. The presence of fully volatile particles has implications for
PM health effects, as inammation and oxidative stress (precursors
to some cardiovascular and respiratory diseases) are more heavily
driven by the presence of organic compounds.

particle-phase PAHs emissions by 23.2%, 14.6%, and 7.7%, respectively. In addition, the particle-phase PAHs concentration related
total BaPeq was still high for Bu10, Bu15 and Bu20 at low engine
load, and for Bu15 and Bu20 at medium engine load, compared
with that from ULSD. This nding is consistent with those previously reported by Chao et al. [31] and Song et al. [32], while conducting their experiments with methanol/ethanoldiesel blends.
Previous studies demonstrated that PAHs are initially in the gas
phase and attach themselves to the particle-phase by diffusion
when the exhaust gas cools, and PAHs in unburned diesel fuel have
been shown to be the primary contributor to particle-phase PAHs
in the exhaust of a direct injection diesel engine [30,33]. The higher
unburned hydrocarbon emissions from butanoldiesel blends have
been reported by previous studies [5,79], which may lead to the
higher PAHs content in particles. This tendency is likely to decrease
when the butanol level in the blends is low and the engine load is
high. Moreover, the higher PAHs content in PM combined with the
lower particulate mass concentration caused by butanoldiesel
fuels as observed in this study may contribute to a reduction of
the particle-phase PAHs concentration in emissions. The two factors conict with each other, making the PAHs emission varied
with the proportion of butanol in blends and engine loads.

3.3. Particle-phase PAHs emissions

3.4. Cytotoxicity of particle extracts
The effects of butanoldiesel blends on the PAHs content in particles expressed as ng/mg (i.e. ng PAHs in mg particles), and the
particle-phase PAHs concentration in exhaust emissions expressed
as lg/m3 (lg particle-phase PAHs emission in m3 exhaust) are
shown in Table 2, respectively. The particle-phase PAHs concentration was calculated based on the PAHs content in particles and particulate mass concentration. In general, the PAHs content
increased, but the corresponding total BaPeq decreased with an increase in engine load. The PAHs contents in particles increased
with engine load as has been reported by Burtscher et al. [30].
Compared to ULSD, Bu5 showed no signicant change in the PAHs
content in particles as well as its total BaPeq. With further increase
in butanol content in blends, PAHs in particles in terms of both total PAHs and total BaPeq increased. From low to high engine load,
the PAHs content increased by 11.133.0%, 13.134.2%, and 5.4
35.8%, while the total BaPeq increased by 31.266.0%, 11.252.0%
and 4.930.9%, respectively corresponding to Bu10, Bu15 and
Bu20. However, the adverse effects of the butanol blended fuels
on PAHs emissions expressed by the particle-phase PAHs emission
concentration (lg/m3) were somewhat reduced due to the reduction of particle mass concentration caused by butanol, as shown
in Fig. 1. This variation is more obvious at high engine load with
a high proportion of butanol in blends due to the high particle
emission reduction at these conditions. However, Bu20 emitted
the highest particle-phase PAHs at all tested engine load conditions. From low to high engine load, Bu20 increased the total

Fig. 3 shows the results of the dose (particle extracts)

response (cell viability) relationship for A549 cells exposed to
serial concentrations of diesel and butanoldiesel particle extracts,
expressed as L/ml (per ml medium containing extracts of particles
collected from L engine emissions). Regardless of fuels used and
the engine load, all the particle extracts caused a dose dependent,
statistically signicant decline in cell viability (p < 0.05) when assessed with the MTT test. In addition, the cell viability decreased
in response to an increase in the engine load from 25% to 75%
while maintaining the same dose, as can be seen in Fig. 3. This
can be attributed to the increase in the OC fraction (see Fig. 1),
which accounts for different classes of organic compounds. The
particle extracts from butanoldiesel blends appeared to be having higher cell viability than those from diesel fuel, especially
when compared between ULSD and Bu10. Seagrave et al.
[34,35], McDonald et al. [36] and Zielinska et al. [37] investigated
the toxicity of particle extracts from a series of gasoline, diesel and
natural gas engine emissions using intratracheal instillation of
these extracts into rats and analyzed their respective chemical
composition. They concluded that the lung toxicity caused by particles was strongly associated with OC and selected organic compounds (hopanes and steranes) that are present in lubricating oil.
More importantly, they found that the chemicals most closely
associated with pulmonary toxicity were different from those
(e.g. PAHs, nitro-PAHs and oxy-PAHs) that were associated with

135

Z.-H. Zhang, R. Balasubramanian / Fuel 118 (2014) 130136

Table 2
Particle-phase PAH emissions from the diesel generator under various conditions.
ULSD
PAHs content in particles (ng/mg)
25% engine load
LMW-PAHs
344.5 14.5
MMW-PAHs
225.6 7.6
HMW-PAHs
45.1 1.2
Total-PAHs
615.1 23.3
Total-BaPeq
24.9 1.0
50% engine load
LMW-PAHs
333.8 12.9
MMW-PAHs
311.3 9.6
HMW-PAHs
29.2 0.8
Total-PAHs
674.2 23.3
Total-BaPeq
18.1 0.7
75% engine load
LMW-PAHs
291.4 11.2
MMW-PAHs
420.2 13.2
HMW-PAHs
15.1 0.4
Total-PAHs
726.6 24.8
Total-BaPeq
8.8 0.3
Particle-phase PAHs emission concentration (lg/m3)
25% engine load
LMW-PAHs
11.10 0.47
MMW-PAHs
7.26 0.25
HMW-PAHs
1.45 0.06
Total-PAHs
19.81 0.76
Total-BaPeq
0.80 0.03
50% engine load
LMW-PAHs
17.54 0.65
MMW-PAHs
16.35 0.50
HMW-PAHs
1.53 0.08
Total-PAHs
35.42 1.23
Total-BaPeq
0.95 0.03
75% engine load
LMW-PAHs
29.57 1.14
MMW-PAHs
42.65 1.35
HMW-PAHs
1.53 0.04
Total-PAHs
73.75 2.53
Total-BaPeq
0.89 0.03

Bu5

Bu10

Bu15

Bu20

334.8 12.3
229.6 6.7
48.5 1.0
612.9 20.0
27.2 0.9

368.2 14.7
259.8 8.3
55.1 1.4
683.2 24.4
32.6 1.2

401.8 15.5
280.4 8.7
63.0 1.7
745.2 25.9
37.6 1.3

448.4 18.2
301.5 9.8
68.2 1.6
818.1 29.6
41.10 1.5

339.6 14.1
318.5 10.2
29.9 0.7
688.0 25.0
18.0 0.6

374.2 15.0
354.3 11.5
34.3 1.0
762.8 27.5
20.9 1.1

409.1 15.8
385.0 12.1
38.8 1.2
832.9 29.0
23.4 0.8

434.2 16.7
425.7 13.8
45.2 1.6
905.1 32.2
27.5 1.0

284.5 11.8
408.9 12.9
15.1 0.3
708.5 25.0
8.1 0.3

304.6 12.2
444.7 13.7
16.8 0.5
766.1 26.4
9.2 0.3

343.9 13.3
504.8 14.9
18.3 0.6
867.0 28.8
9.9 0.4

408.6 15.7
557.7 16.1
20.2 0.8
986.5 32.6
11.5 0.4

10.59 0.39
7.27 0.22
1.50 0.05
19.36 0.64
0.86 0.03

11.44 0.46
8.08 0.26
1.71 0.07
21.23 0.76
1.01 0.04

12.26 0.49
8.55 0.27
1.92 0.05
22.73 0.81
1.15 0.04

13.38 0.56
8.99 0.30
2.04 0.05
24.40 0.91
1.22 0.05

16.45 0.69
15.98 0.52
1.51 0.05
33.94 1.26
0.91 0.03

18.12 0.73
17.16 0.56
1.66 0.04
36.94 1.33
1.01 0.03

18.90 0.72
17.79 0.55
1.79 0.05
38.48 1.32
1.08 0.03

19.47 0.75
19.09 0.62
2.03 0.03
40.59 1.40
1.23 0.04

27.48 1.09
39.50 1.25
1.46 0.04
68.44 2.38
0.78 0.03

27.83 1.12
40.62 1.23
1.54 0.04
69.99 2.39
0.84 0.03

29.66 1.16
43.53 1.28
1.58 0.05
74.77 2.49
0.86 0.03

32.89 1.27
44.90 1.31
1.62 0.06
79.41 2.64
0.93 0.03

70

changes in the chemical composition of OC might be responsible

for the difference in the toxicity as there was no signicant
decrease in the OC fraction as explained in section 3.2. In this
investigation, we found that butanoldiesel blends can effectively
reduce particulate mass concentrations compared to those from
diesel. However, the reduction of the particulate mass emission
rate may not necessarily lead to a substantial reduction of the
toxic effects toward humans if, concurrently, the chemical composition of the particles changes with an increase in the toxicological
potential of the particle extracts.

60

4. Conclusions

100
25% engine load

50% engine load

ULSD
Bu5
Bu10
Bu15
Bu20

90

Cell viability (% of control)

75% engine load

80

50
0

12 15 0 2 4 6 8 10 12 0 1 2 3 4 5 6

Dose (L/mL)
Fig. 3. Effect of particle extracts from different diesel and butanoldiesel blends on
cell viability.

bacterial mutagenicity. Similar results were also found by Perrone

et al. [38] who assessed the chemical characteristics and the toxicological effects of aerosol particles by using MTT method. Thus,
the higher OC emissions obtained from higher engine load may
lead to the lower cell viability. As for the difference in cell viability
between ULSD and blended fuels with the same engine load,

Combustion experiments were conducted on a single-cylinder

direct-injection diesel engine operating on ultralow sulfur fuel
blended with 5%, 10%, 15% and 20% volume of butanol. The effects
of blends on PM2.5 mass, EC and OC concentrations, volatile and
non-volatile particle number and size distributions, the particlephase PAHs emissions, as well as the cell toxicology of particle
extracts were investigated. The following major conclusions can
be drawn from this preliminary study.
(1) Butanol-diesel blends can reduce PM2.5 mass concentration,
with the reduction being more obvious at high engine load
with a high proportion of butanol in blends. The reduction
can mainly be attributed to the EC emission reduction. However, the blends increased the OC fraction in particles as well
as increased EC/OC ratios.

136

Z.-H. Zhang, R. Balasubramanian / Fuel 118 (2014) 130136

(2) For all tested engine loads, butanol-diesel blends can effectively reduce the total number concentration of volatile
and non-volatile particles with a slight decrease in GMD.
However, at low engine load, Bu15 and Bu20 increased volatile and non-volatile particles of less than 15 nm.
(3) The blends with less than 10% butanol showed no signicant
change in the total particle-phase PAHs concentration, and
their corresponding total BaPeq. However, the higher proportion of butanol in blends leads to higher total PAHs
emissions.
(4) In general, all the particle extracts caused a decline in cell
viability with the increased dose and with the increased
engine load while maintaining the same dose. However,
the change in cell viability between ULSD and its blends with
butanol is less obvious.
(5) A detailed chemical speciation of PM2.5, especially the classication of OC into different chemical groups and determination of specic organic compounds, is needed to better
explain the changes in cell viability observed in this study.

Acknowledgements
Zhang Zhi-Hui would like to thank the SingaporePeking
Oxford Research Enterprise (COY-15-EWI-RCFSA/N197-1) for
providing scholarship in support of his doctoral study.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.fuel.2013.10.059.
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