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Atmospheric Environment 41 (2007) 72327240


www.elsevier.com/locate/atmosenv

Effects of biodiesel on emissions of regulated


air pollutants and polycyclic aromatic hydrocarbons under
engine durability testing
Hsi-Hsien Yanga,, Shu-Mei Chiena, Mei-Yu Loa, John Chi-Wei Lanb,
Wen-Chang Luc, Yong-Yuan Kud
a
Department of Environmental Engineering and Management, Chaoyang University of Technology, Wufong, Taichung 413, Taiwan
Biorefinery & Bioprocess Engineering Laboratory, Department of Chemical Engineering and Materials Science, Yuan Ze University, Taiwan
c
Energy and Environment Laboratories, New Energy Technology Division, Industrial Technology Research Institute, Hsinchu 310, Taiwan
d
Diesel Vehicle Section, Environment & Energy Issue Department, Automotive Research & Testing Center, Chunghwa 505, Taiwan

Received 21 February 2007; received in revised form 12 May 2007; accepted 15 May 2007

Abstract
An 80,000-km durability test was performed on two engines using diesel and biodiesel (methyl ester of waste cooking oil)
as fuel in order to examine emissions resulting from the use of biodiesel. The test biodiesel (B20) was blended with 80%
diesel and 20% methyl ester derived from waste cooking oil. Emissions of regulated air pollutants, including CO, HC,
NOx, particulate matter (PM) and polycyclic aromatic hydrocarbons (PAHs) were measured at 20,000-km intervals. The
identical-model engines were installed on a standard dynamometer equipped with a dilution tunnel used to measure the
pollutants. To simulate real-world driving conditions, emission measurements were made in accordance with the United
States Environmental Protection Agency (USEPA) FTP transient cycle guidelines. At 0 km of the durability test, HC, CO
and PM emission levels were lower for the B20 engine than those for diesel. After running for 20,000 km and longer, they
were higher. However, the deterioration coefcients for these regulated air pollutants were not statistically higher than 1.0,
implying that the emission factors do not increase signicantly after 80,000 km of driving. Total (gaseous+particulate
phase) PAH emission levels for both B20 and diesel decreased as the driving mileage accumulated. However, for the engine
using B20 fuel, particulate PAH emissions increased as engine mileage increased. The average total PAH emission factors
were 1097 and 1437 mg bhp h1 for B20 and diesel, respectively. For B20, the benzo[a]pyrene equivalence emission factors
were 0.77, 0.24, 0.20, 7.48, 5.43 and 14.1 mg bhp h1 for 2-, 3-, 4-, 5-, 6-ringed and total PAHs. Results show that B20 use
can reduce both PAH emission and its corresponding carcinogenic potency.
r 2007 Elsevier Ltd. All rights reserved.
Keywords: Long-term driving; Biodiesel; Polycyclic aromatic hydrocarbons; Durability testing; Deterioration coefcient

1. Introduction
Corresponding author. Tel.: +886 4 23323000;

fax: +886 4 23742365.


E-mail address: hhyang@cyut.edu.tw (H.-H. Yang).
1352-2310/$ - see front matter r 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2007.05.019

Recent concerns over the environment, increasing


fuel prices, and scarcity of supply in the last decade
have stimulated interest in the development of

ARTICLE IN PRESS
H.-H. Yang et al. / Atmospheric Environment 41 (2007) 72327240

alternative sources of liquid-fuel energy (Nwafor,


2004). Among the alternatives are biofuels, which
are increasingly examined as potential substitutes
for conventional high-pollutant fuels. Biodiesel, a
replacement for diesel, is easily made from renewable biological sources, such as vegetable oil and
animal fats. Chemically, biodiesel refers to monoalkyl-esters of long-chain fatty acids, and to a
variety of ester-based oxygenated fuels. It can be
used in diesel engines with little or no modication
(Ramadhas et al., 2004).
Many experiments have been carried out worldwide in which researchers replaced diesel fuel with
vegetable oils. Most of them tested either unblended, clean vegetable oil, or blended with diesel
(Ramadhas et al., 2004). More recently, researchers
have begun looking into applying waste cooking oil,
which is vegetable oil used to cook a variety of
foods and which is no longer viable. Huge quantities
of surplus waste cooking oil are available throughout the world. In the United States, the Energy
Information Administration estimates 100 million
gallons per day (Radich, 2006). Taiwan annually
generates 77 tons, of which only about 4% is
retained for industrial use. Some is used in manufacturing soap and as an additive in fodder production.
Large amounts of waste cooking oil are dumped
into rivers and landlls illegally, causing environmental pollution. Recycling waste cooking oil as
fuel in diesel engines would reduce such environmental degradation (Pugazhvadivu and Jeyachandran, 2005), and could be a cheaper alternative to
both diesel and edible vegetable oils, which cost
more than diesel (Usta, 2005).
The conversion of vegetable oils and waste
cooking oil to biodiesel was developed in 1983
when Nye et al. (1983) conducted preliminary tests.
Most studies have concluded that vegetable oils can
be burned for short periods of time in a diesel engine
(Reed et al., 1992; Murayama et al., 2000; Wang
et al., 2000; McCormick et al., 2001). However,
using fresh vegetable oils and waste cooking oil in a
diesel engine for extended periods may result in
severe engine deposits, piston-ring sticking, injector
coking and thickening of the lubricating oil. In
addition, the high viscosity of vegetable oils and
waste cooking oil reduces fuel atomization, increases fuel spray penetration and produces higher
smoke emission (Altin et al., 2001; Pugazhvadivu
and Jeyachandran, 2005; Usta, 2005).
The process of transesterication signicantly
reduces viscosity and enhances biodiesels physical

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properties, however. Esterication transforms the


structure of plant oil by substituting glycerol with
methanol or ethanol, whereas, the fatty acids
remain unaltered relative to their degree of unsaturation. Transesterication modies the relevant
properties of vegetable oils and waste cooking oil so
that they meet the requirements for use in modern
diesel engines (Nwafor, 2004). It has been reported
that the methyl ester processed from vegetable oils
and waste cooking oil for use in diesel engines offers
lower smoke levels and higher thermal efciencies
than clean vegetable oils and waste cooking oil
(Kumar et al., 2003).
Although the viscosity of waste cooking oils can
be reduced by the transesterication process, dieselengine performance and exhaust emission testing
over the long term is needed for further application.
In response to this need, rigorous emission tests
were conducted on two diesel engines, one fueled
with diesel and the other with biodiesel, which was
esteried from waste cooking oil.
Diesel emissions have been considered a potential
health hazard, mainly because it contains polycyclic
aromatic hydrocarbons (PAHs). Some PAHs are
potentially mutagenic and carcinogenic to humans
(IARC, 1987), but only limited studies have investigated PAH emission of biodiesel (Durbin et al.,
2000; Sharp et al., 2000; Cardone et al., 2002;
Kalam et al., 2003; Lin et al., 2006a, b). While more
research is still needed, this study measured PAHs in
diluted exhaust, as well as CO, NOx, HC and
particulate matter (PM) emission data. The inuence of waste cooking oil methyl ester on diesel
exhaust emission and related health risks was also
investigated.
2. Experimental section
2.1. Engines, durability testing procedure and
dynamometer
Two brand-new modern diesel engines (Mitsubishi), identical in model (4M40-2AT1), were
employed in this study. One used diesel as fuel,
while an 80/20 blend of diesel and methyl ester
derived from waste cooking oil was used to operate
the other. The engines had four cylinders with a
bore and stroke of 95 mm  100 mm, and a total
displacement of 2835 cm3. They were turbocharged,
with indirect injection, and a maximum horsepower
and torque of 80.9 kW at 3700 rpm and 217.6 N m at
2000 rpm, respectively.

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The purpose of durability testing is to simulate


real-world deterioration within a short period of
time. Running the engines under high temperature
and mechanical loading is a widely used method to
age the engine within a short time. In this study, the
test procedure was composed of four steps: start,
warm-up, accumulation and shutdown (Table 1).
After warm up, the engine was run at maximum
speed (3700 rpm) for 13 h every day until the
durability test equivalent of 500 h had accumulated.
The accumulation duration can be converted to
actual mileage accumulation based on fuel consumption rate. The accumulation durations of 0,
125, 250, 375 and 500 h are nearly equivalent to 0,
20,000, 40,000, 60,000 and 80,000 km, respectively.
The engines were inspected and maintained following the manufacturers instructions. Air-pollutant
emissions were measured at 40,000 and 80,000 km
both before and after maintenance.
Tailpipe emissions were measured at 0 km, then
every 20,000 up to 80,000 km. Many countries
require durability testing up to a specied mileage
to certify that new vehicle models are in compliance
with emission standards before putting them on the
market. Taiwan requires that engines be tested for
80,000 km to demonstrate compliance.
In this study, United State Environmental Protection Agency (USEPA) FTP transient-cycle procedure was used for air pollutant measurements.
The cycle was carried out twice, with the second
cycle begun with a warm start after a stop of 1200 s
on completion of the rst cycle (cold start). The
emission factors (EF; mg bhp h1 for regulated air
pollutants and mg bhp h1 for PAHs) were calculated according to the following equation:
EF

W
,
bhp h

where W denotes the weight of air pollutants


emitted and bhp h is the brake horsepower-hour
for every test. According to the USEPA FTP
transient-cycle procedure for emission calculation,
the weighting factors are 1/7 for cold-start phase
and 6/7 for warm-start phase. To eliminate measurement variations, two warm-start cycles were run
for each test. Thus, in this study, air pollutant
emission factors were calculated as 1/7 cold-start
phase+6/7 mean of two warm-start phase tests.
The two engines were mounted and operated on a
Schenck DyNAS 335 dynamometer with a DC-IV
control system. The DC-current dynamometer with
a fully automatic control system is capable of
supplying maximum power and torque at 335 kW
and 800 N m, respectively. It is also capable of
switching from positive to negative torque values in
a very short time. This enabled a transient cycle test
to be performed according to the USEPA FTP
transient cycle procedure for measuring air pollutants. The cycle sequence includes the categories of
expressway, congested urban, and uncongested
urban driving. The transient cycle employed is a
government-required procedure in Taiwan, as well
as in the US.
2.2. Fuels
Diesel fuel (supplied by the Chinese Petroleum
Company) and a blended fuel (B20) of 80% diesel
and 20% methyl ester of waste cooking oil (supplied
by Taiwan NJC Corp.) were tested in this study.
Specications of both fuels are listed in Table 2. The
sulfur concentrations shown are 20.5 and
21.8 ppmw for B20 and diesel, respectively. The
data also show that B20 is more viscous than diesel,
because B20 has higher viscosity (3.53 CST) than
diesel (3.15 CST).
2.3. Dilution tunnel and constant volume sampling
system

Table 1
Durability test cycle specications
Steps

Rotational
speed (rpm)

Throttle
width (%)

Duration
(min)

Start
Warm-up

800
1500
2000
3700
2000
1500
800

0
25
50
100
50
25
0

4.0
6.0
3.0
780
3.0
6.0
4.0

Accumulation
Shutdown

The exhaust emission sampling system (HORIBA


CVS-9400T) was operated on the constant volume
sampling (CVS) principle, and double dilution was
used to obtain PM and PAHs. The gaseous
emissions were measured continuously by analyzers.
The computer performed an integration over the
cycle duration as the analyzers collected data. PM
and PAH emissions were collected with a full ow
CFV-type dilution tunnel (HORIBA DLT24150W),
which was 610 mm in diameter. The CVS ow rate

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H.-H. Yang et al. / Atmospheric Environment 41 (2007) 72327240
Table 2
B20 and diesel specications
Fuel parameters

B20

Diesel

Analytical
method

Density (g ml1
at 15 1C)
Flash point (1C)
Viscosity (CST
at 40 1C)
Carbon residue
(mg g1)
Cetane index
Ash (wt%)
Lubricity (mm)

0.84

0.83

ASTM D4052

97
3.53

78
3.15

ASTM D93
ASTM D445

o0.01

o0.01

ASTM D4530

55.7
o0.001
196

53.1
o0.001
332

1A
o0.0005

1A
o0.0005

ASTM D613
ASTM D482
HFRR-diesel
lubricity test
ASTM D130
ASTM D2709

20.5
9978

21.8
10234

ASTM D5453
ASTM D240

Corrosiveness
Water and
residue (vol%)
Sulfur (ppmw)
Heat value
(kcal kg1)

was controlled by a critical ow venturi as it was


drawn into the dilution tunnel by a Spencer blower.
All (100%) of the engine exhaust gas was fed into
the tunnel by a 10 cm diameter and 7.5-m-long solid
insulated pipe, and mixed with the air in a
development section with a length 10 times the
diameter to ensure good mixing and correct emission species development. The dilution factor was
about 25 and the dilution air about 600 m3. The
dilution-tunnel air was adjusted throughout so that,
at the rated power of the engine under testing, the
temperature of the fully diluted exhaust gas did not
exceed 190 1C.
Particulate phase PAHs and PM were collected
by glass-ber lters (diameter 70 mm) at a temperature below 52 1C. A back-up lter was used
downstream of the sampling lters to check breakthrough effects. Two glass cartridge holders were
installed after the back-up lter holder. The glass
cartridge containing a polyurethane foam (PUF)
plug and XAD-16 resin was used to collect the gasphase PAHs. Filter and glass cartridge preparation
has been described in detail elsewhere (Yang et al.,
2005, 2007).
2.4. Analysis of air pollutants
HC was analyzed continuously using a HORIBA
FIA-125 heated ame ionization detector. CO and
CO2 were analyzed by a non-dispersive infrared

7235

instrument (HORIBA AIA-120), and NOx by


chemiluminescence using a HORIBA CLA-155.
The concentrations of the following PAHs were
determined: naphthalene (Nap), acenaphthylene
(AcPy), acenaphthene (Acp), uorene (Flu), phenanthrene (PA), anthracene (Ant), uoranthene
(FL), pyrene (Pyr), cyclopenta[c,d]pyrene (CYC),
benz[a]anthracene (BaA), chrysene (CHR), benzo[b]uoranthene (BbF), benzo[k]uoranthene (BkF),
benzo[e]pyrene (BeP), benzo[a]pyrene (BaP), perylene (PER), indeno[1,2,3,-cd]pyrene (IND), dibenz[a,h]anthracene (DBA), benzo[b]chrysene (BbC),
benzo[ghi]perylene (BghiP) and coronene (COR).
PAH samples were Soxhlet-extracted with a
mixed solvent (n-hexane and dichloromethane,
400 ml l1 each) for 24 h. The extract was then
concentrated by purging with ultra-pure nitrogen to
2 ml for the cleanup procedure. The cleanup
procedure was to remove pollutants which would
coelute with PAHs from the gas chromatography
(GC) column. The bottom of the cleanup column
was lled with glass wool (inner diameter, 1 cm).
Seventeen grams of 6% deactivated silica gel mixed
with 60 ml of n-hexane was loaded into the cleanup
column which was then topped with 1.5 cm of
anhydrous sodium sulfate. Next, 60 ml of hexane
were added to wash the sodium sulfate and the silica
gel. Right before the sodium sulfate layer was
exposed to the air, the hexane elution was stopped
and the eluant was discarded. The concentrated
sample was then transferred onto the column, the
vessel wall was rinsed twice with 2 ml hexane which
was also added to the column. Next, 200 ml of 6%
ethylether in hexane was added to the column and
allowed to ow through the column at a rate of
35 ml min1, and the eluant was collected. The
collected eluant from the cleanup procedure was
reconcentrated to 0.5 ml with ultra-pure nitrogen.
A GC (Agilent 6890) with a mass spectrometric
(MS) detector (Agilent 5973N) and a computer
workstation were used for the PAH analysis. The
GCMS was equipped with: an Agilent capillary
column (Agilent Ultra 2, 50 m  0.32 mm 
0.17 mm); an Agilent 7673A automatic sampler,
with an injection volume of 1 ml, splitless injection
at 310 1C and an ion source temperature at 310 1C.
Oven operating temperature ranged from 50 to
100 1C at 20 1C min1, 100290 1C at 3 1C min1,
and held at 290 1C for 40 min. The masses of
primary and secondary PAH ions were determined
by using the scan mode for pure PAH standards
(Merck). Qualication of PAHs was performed by

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using the selected ion monitoring (SIM) mode.


Authors of this study have described PAH analysis
in detail in a previous report (Yang et al., 2005). In
this study, two internal standards (phenanthrene-d10
and perylene-d12) were used to check the response
factors and the recovery efciencies for PAH
analysis. The recovery efciencies of these two
internal standards and 21 individual PAHs were
determined by processing a solution containing
known PAH concentrations through the same
experimental procedure used for the samples. The
recovery efciencies of the two internal standards
were fairly constant between 83.0% and 88.0%.

3. Results and discussion


3.1. Emission differences of two test engines
Except for the test engines, all experimental
conditions in this study were controlled the same
for B20 and diesel. It is important to compare the
emission differences of the two engines, because the
results can be used to check whether the differences
of emission results are attributed to the fuel or to
engine differences. In this study, the two engines
were both fueled with diesel and the emission results
of regulated air pollutants were compared to verify
the emission differences of the two engines at the
beginning (0 km) and the end (80,000 km) of mileage
accumulation.
The emission factors of regulated air pollutants
and CO2 are listed in Table 3. For the two brandnew engines (0 km), the emission differences for CO,
HC, NOx and CO2 are 3.8%, 5.8%, 9.6% and
3.6%, respectively. After 80,000 km driving, the
emission differences of these two engines are 6.6%,
2.5%, 9.9% and 0.7% for CO, HC, NOx and CO2,
respectively. The emission differences are small for
Table 3
Emission factors of regulated air pollutants for the two engines
both using diesel (g bhp h1)
Air
pollutants
CO
HC
NOx
PM
CO2

At 0 km

At 80,000 km

Engine #1

Engine #2

Engine #1

Engine #2

0.850
0.055
3.91
0.059
833

0.819
0.052
4.33
NA
804

0.784
0.054
3.59
0.066
827

0.840
0.055
3.98
0.097
834

NA: not available.

CO, HC and CO2. For PM emission, however, there


is signicant difference between these two engines
(32%) at 80,000 km. According to the results,
comparison of the PM emission factors for B20
and diesel is not appropriate since the difference
could be attributed to the engines. Only deterioration characteristics for PM emission were compared
in this study.
3.2. Emission factors of regulated air pollutants
The emission factors of regulated air pollutants,
HC, CO, NOx and PM, expressed by mass emitted
per brake horsepower per hour (g bhp h1) are
shown in Fig. 1. For the emissions at 0 km, the
emission factors of CO, HC and NOx for B20 are
0.826, 0.055 and 4.35 g bhp h1, respectively. The
emission factors of CO, HC and NOx for diesel are
0.859, 0.061 and 3.91 g bhp h1, respectively. A large
number of experiments with biodiesel have been
carried out all over the world. Restricting the results
to studies that use the FTP tests yields a consistent
picture of reductions in HC, CO and increase in
NOx for biodiesel (e.g., Sharp et al., 2000; Souligny
et al., 2004; Alam et al., 2004; McCormick et al.,
2005). The trends of these air pollutants in this
study are in agreement with previous studies.
Emission levels of HC, CO and PM at the
beginning of the durability test were lower for B20
than those for diesel. But after running for
20,000 km and longer, the emission levels became
higher for B20 (Fig. 1). The viscosity of B20
(3.53 CST) is higher than that of diesel (3.15 CST)
(Table 2). Previous studies showed that the higher
viscosity of biodiesel can reduce atomization and
then cause higher air-pollutant emission after longterm operation (Pugazhvadivu and Jeyachandran,
2005; Usta, 2005). The higher viscosity of B20 is one
cause for higher air-pollutant emissions for longterm driving compared to diesel. Fuel with higher
viscosity tends to cause deposits in injectors, pump
parts and chambers of the engine, which may result
in incomplete combustion of fuel (Kalam and
Masjuki, 2004). The emissions of HC and CO for
B20 were therefore higher than diesel after longterm driving.
Lin et al. (2006a, b) added three fuels separately
to three brand-new engines for their durability
testsB20 (a biodiesel blend of 20% palm oil and
80% diesel), B100 (100% palm biodiesel) and diesel.
Their emission test procedure was also based on US
transient cycle specications; however, the durability

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B20
Diesel

2.0
CO
1.5

R2= 0.02 (B20)

y= (9x 10-9)x + 0.05

0.08

R2= 0.003 (B20)

HC

0.06

1.0
Emission factors (g bhp-h-1)

0.10

y= (-3 x 10-7)x + 0.82

0.5

y = (8 x

10-7)x

+ 0.81

R2= 0.31 (Diesel)


0.0

0.04

y= (-2 x 10-7)x + 0.06

0.02

R2= 0.55 (Diesel)

0.00
0

20000

40000

60000

80000

20000

40000

60000

80000

0.20
y = (-3 x 10-6)x + 4.39

NOx

R2= 0.35 (B20)

y = (4 x 10-7)x + 0.07
0.15

PM

R2= 0.45 (B20)

4
0.10

y = (-4.8 x 10-6)x + 3.98


R2= 0.62 (Diesel)

0.05

y = (3.7 x 10-8)x + 0.062


R2= 0.22 (Diesel)

0.00

0
0

20000

40000

60000

80000

20000

40000

60000

80000

Running mileage (km)


Fig. 1. Emission factors of regulated air pollutants determined by engine durability test.

test mileage was 18,000 km. The emission factors for


HC, CO, NOx and PM for B20 at 0 km were 0.241,
1.39, 4.88 and 0.114 g bhp h1, respectively. After
running for 18,000 km, the emission factors of these
air pollutants were 0.250, 1.46, 3.77 and
0.117 g bhp h1, respectively. The emissions of HC,
CO and PM increased as running mileage increased.
The results agree with the measurement data at
20,000 km in our study.
3.3. Deterioration coefficients of regulated air
pollutants
The regulated air-pollutant emissions for B20
were higher than diesel after long-term driving.
Looking at all of the measurement data, however,
only PM (both B20 and diesel) and HC (B20 only)
emissions increased as mileage increased (Fig. 1).
We further evaluated the deterioration coefcients
of the four air pollutants according to US CFR,
Title 40, Part 86, Subpart A. First, a regression line
was made for seven measurements for each pollutant (Fig. 1); then, the emission factors for the
regression line at 20,000 and 80,000 km could be
obtained. The deterioration coefcient is the value

of the emission factor at 80,000 km divided by the


emission factor at 20,000 km. For diesel, the
deterioration coefcients of HC, CO, NOx and
PM were 0.81, 0.94, 0.93 and 1.04, respectively. For
B20, the deterioration coefcients were 1.01, 0.98,
0.96 and 1.3 for HC, CO, NOx and PM, respectively. A deterioration coefcient higher than 1.0
implies that air-pollutant emissions would increase
after 80,000 km driving. The above results indicate
that after 80,000 km of driving, PM emission for
diesel, HC and PM emission for B20 will increase.
The statistical signicance of the slopes of these
tted regression lines was determined as described
below.
The deterioration coefcient is applied in order to
estimate air-pollutant emission factors after longterm driving. The air-pollutant emission factors
after 80,000 km driving are the emission factors at
0 km multiplying the deterioration coefcients for a
new model engine only if the deterioration coefcient is higher than 1.0. The statistical parameters
of the regression line slopes are listed in Table 4.
The p-value o0.05 implies the slope is signicantly
different from 0 at a 95% condence level. For
diesel fuel, the p-value of NOx is 0.035, but the

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Table 4
Regression analysis parameters of slope for air pollutants
Air pollutants

CO
HC
NOx
PM
P-PAHs
Total PAHs
BaPeq

B20

Diesel

Coefcient

Standard error

p-value

Coefcient

Standard error

p-value

3  107
9  109
3  106
4  107
0.0019
0.014
2  104

1.2  106
7  108
1.6  106
1.9  107
0.0006
0.005
1  104

0.825
0.906
0.160
0.098
0.026
0.037
0.131

8  107
2  107
4.8  106
3.7  108
0.0043
0.022
7.5  104

5  107
7  108
1.6  106
3  108
0.003
0.010
3  104

0.193
0.054
0.035
0.288
0.171
0.074
0.057

coefcient of the slope is negative (4.8  106).


These results indicate that the emission factors for
all four of these regulated air pollutants do not
increase signicantly for both B20 and diesel
according to statistical analysis.
3.4. PAH emission factors and corresponding
carcinogenic potencies
The PAH emission factors for B20 and diesel
fuels are listed in Table 5. The average total PAH
emission factors were 1097 and 1437 mg bhp h1 for
B20 and diesel, respectively. For most ringed-PAHs
and total-PAHs, B20 has lower PAH emission levels
than that of diesel fuel. Many previous studies have
also shown that biodiesel can reduce PAH emission
(Sharp et al., 2000; Cardone et al., 2002; Kalam
et al., 2003; Lin et al., 2006a, b). Similarly, the
results of this study show a 23.7% reduction in
PAH emissions when B20 was used as fuel.
We further applied toxic equivalency factors
(TEFs) for the 21 analyzed PAHs to assess the
carcinogenic potencies for B20 and diesel. The TEFs
have been devised as a way of comparing the
carcinogenic potency of the individual PAHs with
the carcinogenity of BaP (Nisbet and LaGoy, 1992).
In this study, the TEFs are expressed in terms of its
BaP emission equivalent (BaPeq). The BaPeq factor
for each individual PAH was calculated by multiplying the emission factor with corresponding TEF
values. Table 5 also lists the BaPeq factors for
variously ringed PAHs. For B20, the BaPeq factors
were 0.77, 0.24, 0.20, 7.48 and 5.43 mg bhp h1 for
2-, 3-, 4-, 5- and 6-ringed PAHs. For diesel, the
BaPeq factors were 0.72, 0.36, 1.15, 35.3 and
7.45 mg bhp h1 for 2-, 3-, 4-, 5- and 6-ringed PAHs.
The total BaPeq factors were 14.1 and
45.0 mg bhp h1 for B20 and diesel fuel, respectively,

Table 5
PAH and BaP equivalence emission factors (mg bhp h1)
Ring
number

B20

Diesel

PAHs

BaPeq

PAHs

BaPeq

2-ring
3-ring
4-ring
5-ring
6-ring
7-ring

7667557
197794.1
11.474.61
56.6753.3
60.2745.0
5.7376.86

0.7770.56
0.2470.13
0.2070.20
7.4877.57
5.4373.89
NAa

7227485
2987226
42.0732.1
2007110
125799.0
50.0737.2

0.7270.48
0.3670.26
1.1571.22
35.3724.9
7.4576.04
NA

Total
PAHs

10977494

14.1710.8

14377908

45.0731.3

NA: no toxic equivalence factor was available.

which indicates a 68.7% reduction in total BaPeq


emissions when B20 was used as fuel. These results
show that B20 can reduce not only PAH emission
factors, but also their corresponding carcinogenic
potency.
3.5. Deterioration coefficients of PAHs
Durability-test PAH emission factors are shown
in Fig. 2. For both B20 and diesel, the total
(gaseous+particulate) PAH emission levels decreased as the driving mileage accumulated
(Fig. 2a). However, particulate PAH emissions
increased for B20 as the mileage increased (Fig. 2b).
This is similar to the PM trends (Fig. 1). The PAH
deterioration coefcients were also evaluated by the
same method used for regulated air pollutants. The
total PAH deterioration coefcients were 0.41 and
0.35 for B20 and diesel, respectively. For particulate
PAHs, the deterioration coefcients were 2.61 and
0.43 for B20 and diesel, respectively. The regression
p-value of particulate PAHs for B20 was 0.026

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H.-H. Yang et al. / Atmospheric Environment 41 (2007) 72327240

B20
D100
Total PAHs

8000

Emission factors (g hph-h-1)

6000

y = -0.014 x + 1710

y = -0.022 x+ 2420

R2=

R2= 0.50 (Diesel)

0.62 (B20)

4000
2000
0
Particle phase PAHs

3000
y = 0.0019 x + 33.2

2000

2=

0.66 (B20)

y = -0.0043 x+ 534
R2= 0.34 (Diesel)

1000
0

20000
40000
60000
Running mileage (km)

80000

Fig. 2. Emission factors of PAHs determined by engine


durability tests.

(Table 4). The results indicate that for both B20 and
diesel, total PAH emission levels would not
increase, but B20 would cause higher particulate
PAH emission signicantly with long-term driving.
The deterioration coefcients of total BaPeq are also
listed in Table 4. The total BaPeq deterioration
coefcients were 1.45 and 0.38 for B20 and diesel,
respectively. The regression p-values of total BaPeq
were 0.131 and 0.057 for B20 and diesel (Table 4).
Although the statistical results show that the slopes
were not signicantly different from zero, the trends
were similar to those of P-PAHs. The results are
expected because higher molecular weight PAHs,
which are more carcinogenic, are primarily distributed in particulate phase.
4. Conclusion
Diesel and the B20 blended fuel (20% methyl
ester of wasting cooking oil and 80% diesel) were
separately used in two brand-new modern diesel
engines of identical type for durability test
(80,000 km). For this study, the engines were
mounted and operated on an engine dynamometer.

7239

The exhaust emission sampling system was operated


on a constant-volume sampling principle, and
double dilution was used to obtain PAHs under
US transient cycle test procedure. Emissions of HC,
CO, NOx, PM and PAHs were measured at 20,000km intervals. The results of the durability runs,
using B20 fuel, show average emission factors over
time of 0.056, 0.81, 4.27 and 0.087 g bhp h1 for HC,
CO, NOx and PM, respectively. At 0 km, the
emission factors of HC, CO and PM for B20 were
lower than those for diesel. After running for
20,000 km and longer, B20 emission levels were
higher than diesel. The viscosity of B20 (3.53 CST)
is higher than that of diesel (3.15 CST) and results
show that higher B20 viscosity is a factor causing
higher emission after extended miles of engine
operation. In general, air-pollutant emissions would
increase as mileage accumulated (however, statistically not signicantly).
The average total PAH emission factors were
1097 and 1437 mg bhp h1 for B20 and diesel,
respectively. For most ringed-PAHs and totalPAHs, B20 has lower PAH emission levels than
that of diesel fuel. For both B20 and diesel, total
PAH emission levels decreased as the driving
mileage accumulated. However, particulate PAH
emissions increased for B20 as the mileage increased. Statistical analysis results show that B20
would cause higher particulate PAH emission
signicantly (p 0.026) with long-term driving.
Acknowledgment
This study is in part nancially supported by the
National Science Council of the Republic of China
under Contract No. NSC 95-2221-E-324-010.
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