ARTICLE IN PRESS

Atmospheric Environment 38 (2004) 1631–1640

Emission of polycyclic aromatic hydrocarbons from light-duty

diesel vehicles exhaust
Rui de Abrantesa,*, Jo*ao V. de Assun@*aob, Ce! lia R. Pesquerob
a
* Paulo, Brazil
Vehicular Emission Laboratory, Cetesb, Sao
b
* Paulo, Sao
School of Public Health, University of Sao * Paulo, Brazil
Received 24 July 2003; received in revised form 24 November 2003; accepted 24 November 2003

Abstract

Standardised tests were performed on four light-duty diesel vehicles running in a chassis dynamometer at a vehicular
emission laboratory, using the FTP-75 test cycle procedure. The aim was to characterise emissions of Polycyclic
Aromatic Hydrocarbons (PAHs), substances that create health hazards and are, as yet, unregulated. The pollutants
were analysed in both solid and gaseous phases using high-performance liquid chromatography. Total PAH values
ranged from 1.133 to 5.801 mg km
1. Naphthalene, phenanthrene, fluoranthene, pyrene and chrysene were detected in
all tests. In addition, PAH emission was observed to be inversely related to emission of CO2.
r 2003 Elsevier Ltd. All rights reserved.

Keywords: PAHs; Aromatic pollutants; Vehicular emission; Air pollution; Toxic pollutants

1. Introduction emissions of hydrocarbons and 77% of particulate

All over the world, the numbers of motor vehicles
have been progressively increasing, constituting a global
threat due to the thousands of tons of pollutants they
spew into the atmosphere daily. In addition to worsen-
ing global problems such as the greenhouse effect, these
pollutants have created conditions for the occurrence of
critical air pollution episodes. These episodes occur
mainly in the larger urban centres, affecting the quality
of life and compromising public health, increasing
morbidity and mortality rates, mainly in children and
seniors (Mage and Zali, 1992; Sher, 1998; Saldiva et al.,
2001; WHO, 1996a).
In 2001, the Metropolitan Area of the city of S*ao
Paulo, in the state of S*ao Paulo (Brazil), had a fleet of
seven million motor vehicles. Diesel vehicles represented
6% of this total. However, in addition to contributing to
elevated concentrations of other pollutants, emissions
from diesel vehicles constituted 18.4% of total vehicular
*Corresponding author. Fax: +55-11-3030-6695.
E-mail address: ruia@cetesb.sp.gov.br (R. de Abrantes).
matter emissions, corresponding to 70,600 and
19,700 tons, respectively (CETESB, 2002).
Over the last 10 years, use of school vans, public
transportation and small delivery services in the
Metropolitan Area of S*ao Paulo have increased. As a
consequence, the fleet of light-duty commercial diesel
vehicles1 has shown an impressive growth rate of 7.39%
per year, considerably higher than the global average of
2.6% over the same period (ANFAVEA, 2003).
This rapid growth rate, compared with recent
epidemiological studies, creates new public health
concerns. There is currently no specific regulation of
the emission of Polycyclic Aromatic Hydrocarbons
(PAHs) from motor vehicles (WHO, 1998) despite the
fact that emission of total hydrocarbons and particulate
matter are already regulated in Brazil and in most
industrialised countries (IBAMA, 1998).
1
Light commercial vehicles in Brazil are defined as vehicles
with a maximum total mass of up to 3856 kg, designed to
transport cargo, travel off-road or carry more than 12
passengers (Ibama, 1998).

1352-2310/$ - see front matter r 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2003.11.012
 ARTICLE IN PRESS
1632 R. de Abrantes et al. / Atmospheric Environment 38 (2004) 1631–1640
Consisting of hundreds of compounds that contain
two or more aromatic rings (benzene rings); PAHs in the
air are more commonly in a solid, rather than a gaseous
phase. Some PAHs present carcinogenic potential,
capacity to accumulate in fatty tissue and in other
organic materials, such as particulate matter emitted by
vehicles. These attributes complicate their removal from
the human body (WHO, 1998).
Most of the various PAHs have been analysed by the
International Agency for Research on Cancer. Ben-
zo[a]anthracene, benzo[a]pyrene and dibenzo[a,h]an-
thracene were classified as probably carcinogenic to
humans. Naphthalene, benzo[b]fluoranthene and ben-
zo[k]fluoranthene were classified as possibly carcino-
genic to humans. Researchers were unable to classify
fluorene, phenanthrene, anthracene, fluoranthene, pyr-
ene, chrysene or benzo[ghi]perylene as to their carcino-
genicity to humans. Acenaphthene has not been
analysed (IARC, 2003).
Measurements of PAHs in the atmosphere of the city
of S*ao Paulo taken by Martinis et al. (2002) showed
concentrations of 6400 pg m
3 of benzo[a]anthracene
and 2700 pg m
3 of benzo[a]pyrene, while Vasconcellos
(1996) found 1950 pg m
3 of benzo[a]pyrene and
1031 pg m
3 of benzo[a]anthracene and Mendon@a
(1991) found 3600 pg m
3 of dibenzo[a,h]anthracene. In
addition, in the atmosphere of the city of Rio de Janeiro
(Brazil), Azevedo et al. (1999) found 10670 pg m
3 of
benzo[a]pyrene and 2110 pg m
3 of benzo[a]anthracene.
These values are higher than those found in rural
areas, where values typically ranged from 100
to 1000 pg m
3 (WHO, 1998). In addition, taking
benzo[a]pyrene as an example, these values were higher
than those found in other urban atmospheres, such as
those of Los Angeles, USA (590 pg m
3), La Spezia,
Italy (2200 pg m
3), Julich, Germany (1100 pg m
3) and
Leeds, England (1040 pg m
3) (Martinis et al., 2002).
The WHO (1996b) has adopted the concept of the
Unit Risk Factor, which is used to calculate the risk of
death from cancer after a lifetime of exposure to a
certain concentration level of a particular carcinogen in
the air. For instance, in a population of 1 million
inhabitants exposed to a cncentration of 1000 pg m
3 of
Table 1
Vehicles characteristics
Vehicle Type Vehicles characteristics
Manufacturer/model
A Pick-up Toyota/Hilux 4  4 CS
Ba Van Asia/Topic
C Van Mercedes Benz/Sprinter F 310 D
D Van Mercedes Benz/Sprinter
a
After engine had been rectified.
benzo[a]pyrene over a lifetime, 87 persons will die from
cancer related to that exposure.
Considering the importance of these compounds in
relation to human health, the aim of this work was to
characterise and quantify the more toxic PAHs in the
exhaust of some light-duty diesel vehicles currently in
use, which were not equipped with catalytic converters.
2. Materials and methods
2.1. Sampling
Between June of 2001 and January of 2002, four light-
duty commercial diesel vehicles, three vans and one
pick-up, were submitted to standardised tests using
a model ECE-50 light-duty hydraulic dynamometer
(Clayton) at the Vehicular Emission Laboratory of
Cetesb, the Environmental Sanitation Agency of the
state of S*ao Paulo. Considering the number of diesel
vehicles in Metropolitan Area of the city of S*ao Paulo,
the number of four vehicles represents an error of 40%
with a confidence interval of 64%, so these results must
be considered preliminary (Provost, 1984). The char-
acteristics of the vehicles tested are shown in Table 1.
The vehicles were tested following the cold start
United States Federal Test Procedure 75 (FTP-75), this
standardised conduction cycle is divided in three stages
and simulates urban driving conditions.
In accordance with CFR 40 recommendations
(United States, 1997), exhaust gases were collected after
being mixed and homogenised with the ambient air. A
Critical Flow Venturi-Constant Volume Sampler (Hor-
iba CFV-CVS model 20A) system and a full-flow
dilution tunnel were used. The dilution tunnel consisted
of a stainless-steel duct, whose diameter promoted
turbulent flow conditions in order to homogenise the
mixture of emission and ambient air.
In addition, an ambient air-mixing device that filters
the dilution air through three filters (two for particles
and one for hydrocarbon compounds) was used. In
order to avoid water condensation in the sampling
system, the device was placed as close as possible to the
Year Accumulated Cylinder Power
mileage (km) capacity (l) (kW)
1995 31,182 2.8 64
1995 2831 2.7 55
1997 22,888 3.1 85
1998 43,697 3.1 85
 ARTICLE IN PRESS
R. de Abrantes et al. / Atmospheric Environment 38 (2004) 1631–1640
Fig. 1. Scheme of PAH sampling.
vehicle. The sampling point was positioned at the end of
the dilution tunnel, in the centre, facing upstream, using
isocratic-sampling velocity.
The system collection scheme is shown in Fig. 1. For
each stage of FTP-75, a glass fibre filter Gelman,
porosity 1 mm and 47 mm diameter, was used for
the collection of particulate matter. The maximum face
velocity (20 cm s
1) was adopted, in order to have
sufficient concentrations for each compound of interest,
according method J 1936 (SAE, 1998). Therefore, a
sampling flow rate of 10 l min
1 was used, so as to
achieve a collected sample volume of approximately
108 l in stages one and three and 295 l in stage two.
The particulate matter mass in the filters was
determined gravimetrically by the difference in mass
before and after each test. Before weighing, the filters
were pre-conditioned in a vacuum desiccator with silica
gel for at least 16 h to eliminate humidity. The filters
were weighed on an Ohaus analytical electronic balance,
model AP250D. After the second weighing, the filters
were placed in Petri dishes, wrapped in aluminium foil to
avoid sample degradation from UV light and stored at

17 C until time of extraction.
Gaseous-phase PAHs were collected with pre-washed
XAD-2 Supelpak 20U adsorbent resins (100/50 mg-
Supelco) and the sampling flow rate was 2 l min
1, as
recommended by the manufacturer. Behind the filter
holders, where the sampling lines fork, two calibrated
dry-gas meters (DGMs) registered the volume sampled
in each branch. After sample collection, the sorbent
tubes were sealed, wrapped in aluminium foil and stored
at
17 C until time of extraction. The samples were
never stored for more than 10 days.
1633
The greater part of the mixture, after being filtered,
was stored in inert Tedlars plastic bags for subsequent
determination of the dilution ratio through quantifica-
tion of CO2 emissions. Ambient air was also sampled
and, in order to obtain an accurate assessment of the
emission of the vehicles, the concentration of each
compound was discounted. The ambient air sampling
point was placed just behind the ambient air filters in the
mixing device. Immediately after the end of each test,
the ambient air was sampled at a flow rate of 2 l min
1
for a length of time equal to or greater than that of the
full test (32 min).
Two tests were performed on each vehicle, at intervals
ranging from 12 to 36 h. Vehicle fuel consumption was
also measured by the fuel-weighing method, in accor-
dance with the Brazilian norm NBR 7024 (ABNT,
1990). In order to characterise PAHs emitted into the
atmosphere in real situations, all tests were carried out
with commercial automotive diesel fuel, rather than with
diesel fuel designed for standardised laboratory tests.
2.2. Analysis
Extraction and analysis were performed according to
the recommendations of the method TO-13 (United
States, 1988). Prior to extraction, samples were spiked
with a known mass of surrogate2 standard Decafluor-
obiphenyl (Aldrich Chemical Co., purity X99.5%, CAS
434-90-2). Each sample, including filters and XAD-2
sorbent, was separately extracted by soxhlet over 8 h, at
2
Surrogate standard—a solution containing a compound
that it is not expected to be found in the sample.
 ARTICLE IN PRESS
1634 R. de Abrantes et al. / Atmospheric Environment 38 (2004) 1631–1640

10–15 min reflux time, with 120 ml methylene chloride
(J.T. Baker, HPLC grade, purity >99.8%, CAS 75-09-2).
During extraction, the system was wrapped in alumi-
nium foil to protect the samples against UV light. Blank
filters and sorbents were also extracted for analysis.
All extracts were concentrated to 1 ml using a
Kuderna–Danish evaporator containing two boiling
chips and 3-ball macro Snyder Column and then
increased to a volume of 5 ml with acetonitrile (Carlo
Erba Reagent, HPLC grade, purity >99.9%, CAS
75-05-8).
The analysis was performed by reversed phase high-
performance liquid chromatography (HPLC). The
HPLC system was equipped with two model PU-980
Jasco pumps, a model LC-1250 GBC fluorescence
spectrophotometer and a Waters temperature controller
to maintain the column temperature at 25 C. Separa-
tions were achieved using a reversed-phase Supelcosil
LC-PAH, type O.D.S. - C 18 (15 cm  4.6 ID  5 mm)
and a Supelcosil guard column (Supelco). A mobile-
phase solvent gradient of acetonitrile and deionised
water (50:50) was held isocratically for 5 min, changed
linearly to 100% acetonitrile over 40 min and held in
100% acetonitrile for 5 min. In all analyses, the flow rate
was 1 ml min
1. Excitations and emission wavelengths
that would improve sensitivity and selectivity detection
for each PAH were selected. The analytical parameters
utilised in HPLC analyses are shown in Table 2.
Fourteen PAHs were quantified, namely: naphtha-
lene, acenaphthene, fluorene, phenanthrene, anthracene,
fluoranthene, pyrene, benzo[a]anthracene, chrysene,
benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]
pyrene, dibenzo[a,h]anthracene and benzo[ghi]perylene
(Supelco standards, purity from 93.4% to 99.9%).
Analysis of extracts was performed in duplicate and
concentrations of PAHs were not corrected for surro-
gate recoveries.
The analytical detection limit for each PAH was
considered to be three times the noise level. The linearity
interval of each PAH in the fluorescence detector was
assessed through analysis of nine progressively more
dilute standards, using three injections of each one. By
linear regression, the response of each PAH was
determined, using an r2 higher than or equal to 0.99 as
the criterion. Results are shown in Table 2. To check
instrument performance, a standard solution, with a
concentration greater than 10 times the detection limit
for each PAH, was prepared daily. Analysis of blanks,
including filters and XAD-2 tubes, showed no significant
contamination.
3. Results and discussion
Table 3 summarises the results. The total of the 14
PAHs analysed ranged from 1.133 to 5.801 mg km
1,
with an average of 2.81571.846 mg km
1. The emission
of PAHs in relation to fuel consumption showed that the
simple mathematical average ranged from 8.948 to
55.239 mg l
1, with an average of 24.102717.260 mg of
PAHs per litre of diesel fuel.
Furthermore, with reference to the particulate matter,
values from 0.915 to 3.580 mg of PAHs adsorbed per
gram of particulate matter were found. The data shown
in Table 3 reveal that concentrations of particulate
matter mass emitted during the second test of vehicle C
and during the first test of vehicle D were very low.
These results should be considered with caution since
they have an outlying behaviour, affecting the sum
values of the PAHs in relation to particulate matter and

Table 2
Analytical parameters utilised in HPLC for the analyses of PAHs

Analytical parameters in HPLC

PAHs Excitation (nm) Emission (nm) Linearity interval (mg l
1) Detection limit (mg l
1)

Naphthalene 224 330 10.6–531.0 5.31

Acenaphthene 224 330 1.0–50.0 0.50
Fluorene 224 330 24.8–1242.0 12.42
Phenanthrene 252 370 3.0–302.0 1.51
Anthracene 252 402 1.6–82.0 0.82
Fluoranthene 252 402 34.5–345.0 6.90
Pyrene 238 398 15.2–152.0 3.04
Benzo[a]anthracene 252 402 55.0–550.0 11.00
Chrysene 252 402 5.3–265.0 2.65
Benzo[b]fluoranthene 268 398 23.4–233.5 4.67
Benzo[k]fluoranthene 268 398 5.5–277.0 2.77
Benzo[a]pyrene 268 398 5.8–288.5 2.89
Dibenzo[a,h]anthracene 268 398 6.4–319.0 3.19
Benzo[ghi]perylene 234 420 7.5–377.0 3.77
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R. de Abrantes et al. / Atmospheric Environment 38 (2004) 1631–1640 1635

Table 3
Fuel autonomy, CO2, particulate matter and PAHs emission

Emission rates

Vehicles Test Fuel CO2 emission Emission of Emission of Emission of Amount of

autonomy (g km
1)a particulate PAHs PAHs relative PAHs
(km l
1)a matter (mg km
1)a to fuel adsorved in the
(g km
1)a consumption particulate
(mg l
1) matter
(mg g
1)

Vehicle A 1st Test 9.618 309.9 1.352 5.801 55.239 2.085

2nd Test 9.011 306.5 1.551 5.345 45.888 2.374
Average 9.315 308.2 1.452 5.573 50.564 2.230

Vehicle B 1st Test 6.688 438.2 0.377 1.342 12.828 1.838

2nd Test 6.745 456.5 0.301 1.268 11.936 0.915
Average 6.717 447.4 0.339 1.305 12.382 1.376

Vehicle C 1st Test 7.732 420.4 0.141 1.133 8.948 3.361

2nd Test 7.795 422.5 0.056b 3.112 25.132 12.065b
Average 7.764 421.5 0.141 2.123 17.040 3.361

Vehicle D 1st Test 7.096 427.8 0.025b 2.728 19.366 19.248b

2nd Test 7.127 429.3 0.111 1.793 13.476 3.580
Average 7.112 428.6 0.111 2.261 16.421 3.580

All vehicles Average 7.727 401.4 0.639 2.815 24.102 2.359

Standard 1.071 58.6 0.640 1.846 17.260 0.993
deviation
a
These results are weighted average of three steps of FTP-75, according CFR 40 (United States, 1997).
b
Values considered outlyers.

thereby negating those values, the average was
2.35970.993 mg g
1.
As can be seen in Table 3, vehicle A presented the
highest fuel autonomy: average of 9.315 km l
1, a value
considerably higher than the average of 6.717 km l
1
obtained by vehicle B and the averages of 7.764 and
7.112 km l
1 obtained by vehicles C and D, respectively.
Although vehicle A had presented such good fuel
autonomy, contrary to what had been expected, it
presented the highest particulate matter emission (aver-
age of 1.452 g km
1). It also presented the highest
emission of PAHs per kilometre and PAHs per litre of
fuel consumed (average of 5.573 g km
1 and 50.564 g l
1,
respectively). According to Bosch (1996), diesel vehicles
are normally adjusted to function with more air than is
necessary to create combustion. This situation is known
as a poor mixture because it is poor in fuel. However, as
these tests were made with unmodified in-use vehicles,
we can suggest that vehicle A was working with a richer
air/fuel ratio than the others. In other words, vehicle A
was receiving more fuel than necessary to create efficient
combustion, producing partially combusted fuel and
thereby causing increased formation of particulate
matter and increased PAH emission.
Analysis of variance supported the assumption that
PAH emission varied among the vehicles (ANOVA:
F ¼ 11:3 > Fc ¼ 6:6). In addition, vehicles A and B
displayed more repeatable behaviour, presenting, re-
spectively, 5.8% and 4.0% relative standard deviation in
PAH emissions, whereas vehicles C and D presented
greater variation: 66.0% and 29.3%, respectively.
Despite these differences, the correlation coefficient
observed between emissions of PAHs and those of CO2
was
0.94, showing that there is an inverse correlation
between CO2 emissions and PAH emissions. Therefore,
considering that high CO2 gas emission is directly
related to appropriate combustion, it can be assumed
that efficient combustion proportionates low PAH
emissions (Sher, 1998).
3.1. Individual polycyclic aromatic hydrocarbons results
The results from the analysis of each PAH are shown
in Table 4. All 14 PAHs studied were detected and
quantified in at least three of the eight tests performed.
Five PAHs (naphthalene, phenanthrene, fluoranthene,
pyrene and chrysene) were present in all tests performed.
The other PAHs exhibited irregular behaviour and, in
 ARTICLE IN PRESS
1636 R. de Abrantes et al. / Atmospheric Environment 38 (2004) 1631–1640

Table 4
Emission rates of Individual PAHs, in mg km
1

Emission rates of Individual PAHs (mg km
1)

Compound Vehicle A Vehicle B Vehicle C Vehicle D

1st test 2nd test 1st test 2nd test 1st test 2nd test 1st test 2nd test

Naphthalene 2503.29 1450.47 738.35 963.52 403.64 2012.74 1702.78 1005.15

Acenaphthene 35.84 16.55 2.03 14.70 ND ND 1.52 ND
Fluorene 242.32 157.51 ND 15.75 ND ND ND ND
Phenanthrene 844.26 972.71 159.52 131.58 310.54 867.91 668.83 518.28
Anthracene 33.28 40.30 20.31 11.47 ND ND 0.28 0.82
Fluoranthene 1557.70 2073.66 88.77 29.08 137.20 100.92 138.18 138.99
Pyrene 108.75 51.63 144.44 67.14 277.48 126.01 177.04 121.65
Benzo[a]anthracene 239.68 326.66 35.55 ND ND ND 28.25 ND
Chrysene 35.11 74.71 43.51 7.72 2.19 2.61 4.37 4.24
Benzo[b]fluoranthene 100.63 103.86 17.88 ND 0.74 0.89 1.89 0.42
Benzo[k]fluoranthene 7.41 3.82 14.47 16.16 0.41 ND 1.52 ND
Benzo[a]pyrene 21.20 20.78 28.25 4.38 ND ND 1.22 ND
Dibenzo[a,h]anthracene 53.68 21.05 28.11 ND 0.38 ND 2.11 3.33
Benzo[ghi]perylene 17.43 31.03 20.92 6.34 ND 1.30 ND ND

ND—Not detected.

Naphthalene Table 5 shows some PAHs identified by other authors.

Phenanthrene
Fluoranthene As can be seen, of the 14 PAHs studied in this work,
Average of naphthalene plus fluoranthene
80 only a few of them were detected in previous studies,
70
68

whereas this study was able to detect them all, although

66

70
65

63

60

Rogge et al. (1993) and Westerholm et al. (1991)

57

60
evaluated just the PAHs adsorbed in the particulate
Percentage

50
40 matter. The six gasoline powered vehicles without
35

33

catalytic converters tested by Rogge et al. (1993) were

28

26

30
evaluated in same test cycle (FTP-75), anthracene,
16

20
11

10 fluoranthene, benzo[a]anthracene and dibenzo[a,h]

6
6
5

0 anthracene presented the same order of magnitude than

Vehicle A Vehicle B
Fig. 2. Relative participation of most frequent PAHs in
relation to the sum of PAHs studied.
some cases, were not detected. On average, the sum of
naphthalene, phenanthrene and fluoranthene emission
rates amounted to 87% of total PAH emissions.
Fig. 2 shows the relative participation of the most
frequent PAHs in relation to the sum of 14 PAHs
studied. Regularity in the percentile emission of the most
frequent PAHs in relation to the sum of PAHs is
evident. Naphthalene participation averaged 54% in
relation to the sum of PAHs. Similarly, phenanthrene
and fluoranthene averaged 20% and12%, respectively.
Again, only vehicle A presented behaviour which was
quantitatively different than the other vehicles, emitting
a lower percentage of naphthalene and a higher
percentage of fluoranthene. However, the sum of relative
participation of naphthalene and fluoranthene in rela-
tion to the sum of PAHs was comparable for all vehicles,
with an average sum of 66.6% and relative standard
deviation of 4.7%.
Vehicle C Vehicle D the lower values founded in this work, but phenanthrene
and pyrene presented lower values than this work, by
contrast benzo[k]fluoranthene, benzo[a]pyrene and ben-
zo[ghi]perylene showed higher values, probably due to
the fact that gasoline-powered vehicles operate on richer
mixtures than diesel vehicles, although diesel fuel has a
higher PAHs content compared to gasoline. As ex-
pected, the seven gasoline powered vehicles with
catalytic converters, evaluated in same conduction cycle,
presented lower PAHs values.
Trucks tested by Rogge et al. (1993) and by
Westerholm et al. (1991) also presented lower values
and in some cases showed the same order of magnitude
than the lower values founded in this work, these
deviations can be attributable to differences among in
motor power, piston displacement, accumulated mileage
and especially to the conduction cycle.
The eight different diesel fuels tested in a bus and
in a truck by Westerholm and Li (1994), showed wide
variations in PAH emissions, indicating that fuel
chemical composition influences PAH emission. Max-
imum values of anthracene, fluoranthene, pyrene,
chrysene and benzo[b]fluoranthene also presented the
 ARTICLE IN PRESS
R. de Abrantes et al. / Atmospheric Environment 38 (2004) 1631–1640 1637

Table 5
Comparison of PAH emission with results from others studies, in mg km
1

Emission rate (mg km
1)

Compound This worka Rogge et al., 1993b,d Westerholm et al. (1991)c,d Westerholm and Li, 1994e

b1 b2 b3

Phenanthrene 131.5–972.7 17.3 0.88 12.2 29 0.12–86

Anthracene 0.2–40.37 5.1 0.11 1.6 3.3 0.011–15
Fluoranthene 29.1–2073.7 48.3 2.0 13.0 17 8.8–45
Pyrene 51.6–277.5 31.0 2.5 22.6 11 10–54
Benzo[a]anthracene 28.2–326.7 73.8 1.9 3.6 0.47 0.49–4.1
Chrysene 2.2–74.7 2.8 0.1–3.2
Benzo[b]fluoranthene 0.4–103.9 0.021–1.1
Benzo[k]fluoranthene 0.4–16.2 40.7 2.0 2.7
Benzo[a]pyrene 1.2–28.2 43.5 1.9 1.3 o0.06
Dibenzo[a,h]anthracene 0.4–53.7 8.3 0.33 ND
Benzo[ghi]perylene 1.3–31.0 145.4 4.70 1.6 o0.13 0.012–0.34

ND—Not detected.
a
Three Vans and one pickup fuelled with commercial diesel, cycle FTP-75.
b
(b1)—six Non catalyst cars fuelled with gasoline, cycle FTP-75. (b2)—seven Catalyst car fuelled with gasoline, cycle FTP-75. (b3)—
two Trucks fuelled with diesel, cycle Idle 40 and 70 km h
1.
c
One Truck fuelled with diesel, bus cycle.
d
Authors that Informed just PAHs present in solid phase.
e
One bus and one truck fuelled with 8 different diesel, bus cycle.

same order of magnitude than the lower values detected
in vehicles tested in this study. However, the differences
above cited, like motor characteristics and test condi-
tion, must be taken into account.
Emission profiles of PAHs can be affected by fuel
chemical composition and test cycle (Westerholm and
Li, 1994; Mi et al., 2000). In addition, atmospheric PAH
profiles can be affected by meteorological variables such
as UV light and temperature, furthermore half-lives of
these compounds in the atmosphere vary (Martinis et al.,
2002; WHO, 1998). Despite these facts, some authors
consider the ratios between some of these compounds as
‘‘fingerprints’’ of emission sources (Khalili et al., 1995;
Li and Kamens, 1993).
Table 6 shows the ratios found in this work and those
calculated from other studies. The gasoline-fuelled
vehicles evaluated by Rogge et al. (1993) presented
generally lower ratios; only the ratios between benzo[-
ghi]perylene and benzo[a]pyrene (1.62 for vehicles with
catalytic converters and 3.84 for vehicles without) were
higher than the average ratio found in this study (1.13).
Diesel-powered vehicles presented different ratios too,
including those tested by Westerholm and Li (1994),
with wide variability in these ratios in relation to fuel
composition, in short the PAH ratios as ‘‘fingerprints’’
of motor vehicles must be taken with care.
In spite of disparities among the vehicles in this
study, the ratio between benzo[a]anthracene and ace-
naphthene (15.63) and the ratio between chrysene and
benzo[a]pyrene (2.43) showed a small relative standard
deviation: 39% and 44%, respectively. In addition, only
the ratio between benzo[ghi]perylene and benzo[a]pyrene
(1.13735%) was very close to that found by Martinis
et al. (2002) (1.11), whose sample site was in the city of
S*ao Paulo, where vehicular emissions probably are the
main source of PAHs. We suggest more studies to
confirm if these ratios can be considered good ‘‘finger-
prints’’ for motor vehicles.
3.2. Distribution of PAHs between the solid and gaseous
phase
Fig. 3, in log scale, shows the average emission
of PAHs by test found in solid and gaseous phases.
On average, the PAH mass adsorbed in the particulate
matter was 21.5 mg, while 31.4 mg was present in
the gaseous phase corresponding to 40.6% and 59.4%,
respectively. Lower molecular weight PAHs, such
as naphthalene and acenaphthene, were in higher
concentrations in the gaseous phase (99.8% and
73.0%, respectively). Those of intermediate molecular
weight were present in both phases; relative values in the
solid phase were: fluorene: 56.7%; phenanthrene:
64.1%; anthracene: 83.7%; fluoranthene: 99.0%; and
pyrene: 78.7%. Higher molecular weight PAHs were
predominantly adsorbed in the soot particles, such
benzo[a]anthracene: 100%; chrysene: 98.6%; benzo[b]
fluoranthene: 97.5%; benzo[k]fluoranthene: 100%; ben-
zo[a]pyrene: 100%; dibenzo[a,h]anthracene: 96.5%;
benzo[ghi]perylene: 100%. Following IARC (2003)
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1638 R. de Abrantes et al. / Atmospheric Environment 38 (2004) 1631–1640

Table 6
Comparison of PAH ratios with others studies

PAH ratios

This worka Rogge et al. (1993)b Westerholm Westerholm and Martinis

et al. (1991)c Li (1994)d et al. (2002)e
Average RSD (%) b1 b2 b3

Benzo½aanthracene 15.63 39
Acenaphthene
Fluoranthene: 5.06 37 0.65 1.05 3.61 36.17 10.98–36.54
Benzo½aanthracene
Pyrene: 34.71 179 0.82 0.86 7.79 4.70
Benzo½apyrene
Benzo½aanthracene: 12.87 71 1.95 0.66 1.24
Benzo½apyrene
Chrysene: 2.43 44
Benzo½apyrene
Dibenzo½a; hanthracene: 1.57 46 1.15 0.66 0.45
Benzo½apyrene
Benzo½ghiperylene: 1.13 35 3.84 1.62 0.55 1.1
Benzo½apyrene
Anthracene: 1.50 29 0.04 0.02 1.00 0.32–533.33
Benzo½ghiperylene
Chrysene: 1.95 23 0.38–91.67
Benzo½ghiperylene
a
3 Vans and 1 Pickup fuelled with commercial diesel, cycle FTP-75.
b
(b1)—calculated from Rogge et al. (1993) data—6 non catalyst cars fuelled with gasoline , cycle FTP-75.(b2)—calculated from
Rogge et al. (1993) data—7 catalyst car fuelled with gasoline, cycle FTP-75. (b3)—calculated from Rogge et al. (1993) data—2 trucks
fuelled with diesel, cycle Idle 40 and 70 km h
1.
c
Calculated from Westerholm et al. (1991) data—1 truck (14.19 l) fuelled with diesel, bus cycle.
d
Calculated from Westerholm and Li (1994) data—1 bus (11 l) and 1 truck (9.6 l) fuelled with 8 different diesel fuels, bus cycle.
e
Calculated from Martinis et al. (2002) data—Atmospheric sampling urban site.

100000
Solid phase
10000 Gaseous phase
Average (ug/test)

1000

100

10

1
Benzo[a]anthracene

Benzo[b]fluoranthene

Benzo[k]fluoranthene

Benzo[a]pyrene

Dibenzo[a,h]anthracene
Acenaphthene

Phenanthrene

Anthracene

Fluoranthene

Pyrene
Naphthalene

Fluorene

Chrysene

Benzo[ghi]perilene

Fig. 3. PAHs average emission in mass by test, separated by gaseous and solid phase.
 ARTICLE IN PRESS
R. de Abrantes et al. / Atmospheric Environment 38 (2004) 1631–1640
classification, we were able to verify that the more highly
carcinogenic PAHs, with the exception of naphthalene,
are predominantly adsorbed in the particulate matter.
4. Conclusions
This study has profiled the principal PAH emissions
of four light-duty commercial vehicles powered by
commercial diesel fuel and without catalytic converters.
The sum of fourteen PAHs presented an average
of 2.81571.846 mg km
1, ranging from 1.133 to
5.801 mg km
1. Moreover, PAH emissions ranged from
0.915 to 3.580 mg per gram of particulate matter and
from 8.948 to 55.239 mg/l of fuel consumed.
All 14 PAHs studied were detected and quantified in
at least three of the eight tests performed. Naphthalene,
phenanthrene, fluoranthene, pyrene and chrysene were
detected in all tests. The sum of median emission rate of
naphthalene, phenanthrene and fluoranthene amounted
to 87% of the PAHs detected. In addition, the sum of
naphthalene and fluoranthene emissions proved to be
generally constant for all vehicles, with an average of
66.6% and relative standard deviation of 4.7%.
In general, comparisons with studies by other authors
(Rogge et al., 1993; Westerholm et al., 1991; Westerholm
and Li, 1994), showed that the vehicles evaluated in this
work presented higher PAH emission, except the gaso-
line-powered vehicles without catalytic converters that
emitted practically the same order of magnitude (Rogge
et al., 1993). Furthermore, it was possible to verify that
conduction cycle affects PAH emission and also the
ratios between some PAHs. ‘‘Fingerprints’’ of PAHs
emission from motors vehicles can be affected by many
variables, and only could be considered after detailed
evaluation. In this work, only the ratio between
benzo[ghi]perylene and benzo[a]pyrene was close to the
ratio observed in the atmosphere of the city of S*ao Paulo
by Martinis et al. (2002) (1.1), indicating that further
studies are needed to evaluate if this ratio could be a
good ‘‘fingerprint’’ for diesel vehicles.
On average, emission by test was 21.5 mg in the solid
phase and 31.4 mg in the gaseous phase, corresponding
to 40.6% and 59.4%, respectively. The PAHs with
higher carcinogenic potential are predominantly ad-
sorbed in the particulate matter.
A negative correlation of
0.94 was observed between
CO2 emission and PAH emission.
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