Atmospheric Environment 97 (2014) 195e205

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Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv

On-road and laboratory investigations on non-exhaust ultrafine

particles from the interaction between the tire and road pavement
under braking conditions
Jihyun Kwak a, Sunyoup Lee b, Seokhwan Lee b, *
a
Accident Response Coordination Division, National Institute of Chemical Safety, 90, Gajeongbuk-ro, Yuseong-gu, Daejeon 305-343, Republic of Korea
b
Department of Engine Research, Korea Institute of Machinery and Materials, 156, Gajeongbuk-ro, Yuseong-gu, Daejeon 305-343, Republic of Korea

h i g h l i g h t s g r a p h i c a l a b s t r a c t

We investigate the physical and

chemical characterization of non-
exhaust particles.

Ultrafine particles were measured
during on-road driving and in a
laboratory.

The particle number and size distri-
butions were observed under various
conditions.

The morphological and elemental
analyses can inform the particle
formation.

a r t i c l e i n f o a b s t r a c t

Article history: We investigated the physical and chemical characteristics of non-exhaust ultrafine particles from on-
Received 17 March 2014 road driving and laboratory measurements using a mobile sampling vehicle. The on-road driving and
Received in revised form laboratory measurements during constant speed conditions revealed no enhancement of ultrafine par-
31 July 2014
ticles. Under braking events, the total number concentrations of tire particles (TPs) sampled 90 mm
Accepted 1 August 2014
Available online 6 August 2014
above the road surface was 6 times higher with broader mode diameters when compared to 40 mm
above the road surface. In contrast to braking events, under cornering conditions, the total number
concentrations of TPs sampled 40 mm above the road surface were 50 times higher relative to 90 mm
Keywords:
Tire particles (TPs)
above the road surface. From the morphological and elemental analyses, it is likely that the ultrafine
Brake particles (BPs) particles generated from the interaction between the tire and the road surface under braking conditions
On-road driving might originated from sulfur-containing materials or anti-oxidants which are contained in TPs, and/or
Laboratory measurement graphite and solid lubricants which are mainly present in brake particles (BPs). However, Zn which was a
Morphological and elemental analyses distinguishing elemental marker of tire wear particles didn't show in EDS spectra. Further research
would be required as to the exact emission source of ultrafine particles.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction

Ambient ultrafine particles (<100 nm) are known to affect the

Earth's climate and human health. These particles were found to be
* Corresponding author.
involved in scattering and absorbing solar radiation or in acting as
E-mail addresses: kkjh5950@korea.kr (J. Kwak), sunylee@kimm.re.kr (S. Lee), cloud condensation nuclei (IPCC, 2007). In addition, there have
shlee@kimm.re.kr (S. Lee). been strong relationships between exceeding concentrations of the

http://dx.doi.org/10.1016/j.atmosenv.2014.08.014
1352-2310/© 2014 Elsevier Ltd. All rights reserved.
196 J. Kwak et al. / Atmospheric Environment 97 (2014) 195e205
ultrafine particles and adverse health effects such as increasing
mortality (Ezzati et al., 2002; Ibald-Mulli et al., 2002), as well as
increased respiratory and cardiovascular disease (Hoek et al., 2002;
Peters et al., 2001; Pope et al., 2002). Several studies reported that
nano-size particles are more toxic than their larger counterparts of
same materials and complex interactions between the particles and
gaseous components may act synergistically to increase their toxic
effects (Biswas and Wu, 2005; Faux, 2003).
A number of studies have reported that significant quantities of
ultrafine particles were emitted from exhaust gases of diesel en-
gines or alternatives to conventional base diesel vehicles (Holme
n
and Ayala, 2002; Kittelson et al., 2006; Xinling and Zhen, 2009).
However, as the control regulation for diesel exhaust resulted in a
reduction in emissions from individual vehicles, the relative
contribution from non-exhaust sources such as tire particles (TPs)
emitted from the interaction between the tire and the road surface,
and brake particles (BPs) is increasing (Dahl et al., 2006; Gustafsson
et al., 2010; Mathissen et al., 2011; Kumar et al., 2013). Dahl et al.
(2006) determined the size distributions of ultrafine particles of
studded and non-studded tires depending on different types of
pavements using a road simulator. They reported that the mean
particle diameters emitted from the tires ranged between 15 and
50 nm with highest number concentrations in studded tires and
these particles presumably originated from the tire and not the
pavement. However, in the study of Gustafsson et al. (2010), they
found that ultrafine particles of size 30e50 nm only occur during
tests with studded tires and the major contributor of ultrafine
particles is pavement wear than tire wear. In the study of Mathissen
et al. (2011), on-road measurements of ultrafine particles were
investigated from the tireeroad interfaces and near the brake pad
on different driving conditions using summer tires and revealed
that the nanoparticle numbers significantly increased near the
tireeroad interface and brake pad during braking events.
In addition to investigating tire-related ultrafine particles, several
authors have characterized brake-related ultrafine particles.
Kukutschova
et al. (2011) investigated wear particles released from
“low-metallic” automotive brake pads using brake dynamometer
tests and reported that airborne wear particles had size ranges from
10 nm to 20 mm and the numbers of ultrafine particles (<100 nm) were
by three orders of magnitude larger when compared to the micro-
particles. In addition, the authors emphasized that since the friction
process involves heat and high pressures on the friction interface, the
structure and chemistry of released particles differs from the bulk
friction material of the brake. Garg et al. (2000) and Sanders et al.
(2003) also performed similar brake wear study using a brake dyna-
mometer and observed large particle number concentrations.
However, no attempt has been made to simultaneously investigate
the ultrafine particles produced from the tire and the brake in both on-
road driving and laboratory measurements. Thus, in this study, on-
road measurements were conducted to investigate the physical and
chemical characteristics of ultrafine particles in different driving sit-
uations (constant speed, braking, and cornering). In addition, the ef-
fect of the sampling location from the interaction between the tire and
road surface on the size distributions or number concentrations
of ultrafine particles was considered. The on-road measurements
were compared to those obtained from a road simulator study to
identify the exact sources and to better understand the generation
mechanism of ultrafine particles emitted from the tire or the brake.
2. Experimental methods
2.1. Mobile sampling vehicle
A schematic of the mobile sampling vehicle employed in this
study is provided in Fig. 1. The current mobile sampling vehicle
employed in this study has been well described in previous
research (Kwak et al., 2013a). The vehicle has an unloaded weight of
1400 kg and is powered by a 2000 cc gasoline engine. Because
studded tires are not used in South Korea, all the experiments were
conducted using summer tires (Kumho KH25 225/45/R18, UTQG
(Uniform Tire Quality Grade Standards) tread wear 480). Sampling
inlets were installed in front of the vehicle to measure background
reference concentrations (Fig. 1(1)), behind the front tire to mea-
sure particles generated from the interaction between the tire and
road surface (here defined as tire particles, TPs) (Fig. 1(2)), and close
to the brake pad to sample particles produce by brake wear and
perhaps other materials generated from the tire/road interface
during braking conditions (here defined as brake particles, BPs)
(Fig. 1(3)). Despite being defined as the particles generated from the
tireeroad surface interaction, the TPs may be influenced by various
sources such as tire, brake, road surface wear, road dust, and at-
mospheric depositions, etc. and sampled together with them. In
particular, to investigate the effect of the sampling location on the
size distributions or number concentrations of TPs, the sampling
inlets were installed 40 mm (the minimum height as close as
possible with the road surface without touching) and 90 mm (as far
as possible with the road surface considering the space constraints)
above the road surface, respectively. The brake pad used in our
mobile sampling vehicle is non-asbestos organic (NAO) type and
typically comprises binders, fibers, fillers, lubricants, and modifiers
(Kim et al., 2007). The differences between (2) and (1) or between
(3) and (1) were considered as the net particle number concen-
trations of TPs or BPs, respectively.
All sampling inlets were connected to sampling plena, which
had an inner diameter of 48 mm, and an air flow velocity of 0.58 m/
s with the Reynold's number of 1858 (laminar flow). The ultrafine
particles were drawn with a flow rate of 63 L/min3 (LPM) by a pump
connected to the sampling plena and measured by different
particle-monitoring instruments. Conductive tube with an inner
diameter of 10 mm and length of 1 m was used for lining from the
plenum to particle monitors.
2.2. Sampling site and driving condition
For on-road measurements, it is important to maintain constant
vehicle speed and to exclude the emissions from nearby vehicles
which can aggravate the reliability of our measurements. Thus, all
the experiments were conducted on a high-speed circuit and round
track at the Korea Automobile Testing & Research Institute (KATRI)
proving ground in Hwaseong, South Korea. The proving ground was
constructed in 2002 and is made of asphalt concrete (KSF2349,
<19 mm), which is a mixture of small stones, sands, filler and
bitumen. The proving ground is outside the metropolitan area and,
thus is free from the anthropogenic air pollution sources.
In the high-speed circuit having a 5.5 km distance, “constant
speed driving” and “braking” conditions were conducted. In the
“constant speed driving”, constant driving conditions with no
steering movements of 50, 80, 110, and 140 km/h were tested.
Under “braking” condition, the vehicle gradually starts from 0 to
150 km/h with acceleration rate of 0.54e1.54 m/s2 and stops with
deceleration rate of 2.87e4.16 m/s2. In the round track with a
diameter of 50 m, “cornering” was performed with constant ve-
locity of 50 km/h and a lateral acceleration of 5.1 m/s2. All on-road
measurements at the high-speed circuit and the round track were
repeated at least three times (n ¼ 3), and performed on 15 June
2012 and 13 August 2013. The average temperature and the relative
humidity were 23  C and 65% on 15 June 2012, and 30  C and 75%
on 13 August 2013.
In the proving ground, it is difficult to exclude previously
deposited particles on the road; hence, we performed the road
 J. Kwak et al. / Atmospheric Environment 97 (2014) 195e205
Fig. 1. (a) Photograph showing two sampling sites: KATRI proving ground (left), and road simulator (right), and (b) schematic of the current mobile sampling system, which is based
on the TRAKER designed by Kuhns et al. (2001), employed in this study.
simulator study to compare the properties of TPs and BPs with
those from the proving ground experiments. For this road simula-
tion, the two front tires of our mobile vehicle were fixed onto the
roller of a chassis dynamometer. A sandpaper having a medium-
coarse (80-grit, average particle size 201 mm) abrasiveness was
used for the surface of the roller to simulate asphalt pavements
following the SAE J1269 procedure (NRC, 2006). It was confirmed
that the main component of sandpaper abrasive material was
aluminum oxide by SEM/EDX analyses. In the road simulator study,
same “constant speed driving” and “braking” conditions were
investigated as those used in the on-road measurements. No major
ventilation system in the road simulator hall was adopted, thus no
turbulence was observed. However, some of the generated TPs and
BPs were suspended and affected the background concentration.
The air in the hall was ventilated after each experiment to minimize
the interferences by the particles from the previous experiment.
2.3. Instrumentation
Particle number concentration and size distribution of TPs and
BPs were continuously measured using a fast mobility particle sizer
197
(FMPS, TSI 3091) (6e523 nm). The FMPS has an aerosol flow rate of
10 L/min and a sheath air flow rate of 40 L/min with a particle
number detection range of 103e108 #/cm3. The FMPS measures
particle size distributions every one second and its fast response
enables rapid determination of particle size distributions during on-
road driving. The FMPS software (version 2.1, TSI Inc.) was used for
data collection. The diffusional losses inside the FMPS are assumed
to be insignificant due to the high sample flow rate and low resi-
dence time of particles within the instrument (Asbach et al., 2009).
In order to investigate the morphology and elemental compo-
sition of ultrafine particles emitted from on-road driving and road
simulator measurements, transmission electron microscopy (TEM)
(FEI TECNAI G2F30, USA) with EDAX genesis Energy Dispersive
Spectroscopy (EDS) was used. During braking events, the particles
selected by the differential mobility analyzer (DMA) were collected
at a flow rate of 0.3 LPM on TEM grids using a mini particle sampler
(MPS, Ecomesure, Janvry, France). A condensation particle counter
(CPC) was placed downstream of the MPS to estimate the number
of particles collected on the grids.
The TEM grid used in this study was carbon film-coated 200
mesh copper grid (Ted Pella Inc.) and SiO film-coated 300 mesh
198 J. Kwak et al. / Atmospheric Environment 97 (2014) 195e205
copper grid (Ted Pella Inc.). The collected samples were stored in a
polystyrene Petri dish and equilibrated in a desiccator. The TEM
was operated at a 300 kV accelerating voltage and 1 nA beam
current. TEM images were recorded along with the EDS spectra. The
crystallinity of the particles was also investigated from the selected
area electron diffraction pattern. The background signals of the
TEM grid were corrected by measuring the spectrum of the blank
areas.
3. Results and discussion
3.1. Constant speed driving
Particle number size distributions of TPs measured at the
proving ground and road simulator during constant speed driving
are shown in Fig. 2(a) and (b), respectively. Note that both TPs were
sampled 40 mm above the road surface on 15 June 2012. The
average background total particle concentration on the proving
ground was 2.2  104 ± 7.9  102 #/cm3. The average total particle
concentrations of TPs at vehicle speeds of 50, 80, 110, and 140 km/h
on the proving ground ranged from 2.3  104 #/cm3 to 2.5  104 #/
cm3, indicating of little increase of the particle concentration when
compared to the background value. This is consistent with previous
study by Mathissen et al. (2011), who observed the generation of
ultrafine particles from the tireeroad interface during real world
driving and reported no particle concentration enhancement dur-
ing steady straight driving.
Fig. 2. Particle number size distributions of TPs measured at (a) the proving ground
and (b) road simulator during constant speed driving on 15 June 2012. Both TPs were
sampled 40 mm above the road surface. Constant speed: 50, 80, 110, and 140 km/h.
In contrast to on-road measurements, the average total particle
concentrations of TPs obtained from the road simulator increased
slightly according to vehicle speed and ranged from 2.1  104 #/cm3
to 4.7  104 #/cm3 (Fig. 2(b)). This may be explained that TPs on the
proving ground are easily released to the surrounding atmosphere,
while those from the road simulator are likely to be retained in the
hall due to no major ventilation (Thorpe and Harrison, 2008).
Smaller mode diameter (30e40 nm) of background concentrations
at the road simulator than the proving ground (60e70 nm) might
attribute to different sampling sites.
3.2. Braking conditions
Particle number size distributions and total particle concentra-
tions of TPs measured at the proving ground and road simulator
during braking conditions are shown in Fig. 3(a) and (b), respec-
tively. Note that for both cases, TPs were measured behind the front
tire on 15 June 2012 and the sampling inlets were positioned
40 mm above the road surface. Under the deceleration conditions,
the total number concentrations of both TPs significantly increased
and were 30e40 times higher than those under constant speed
driving. This result is consistent with previous works by Lee et al.
(2004) and Mathissen et al. (2011). According to the report by
Luhana et al. (2004), an aggressive driving style such as accelera-
tion, braking, and cornering tended to result in more tire particles.
The TPs observed from both the proving ground and road simulator
had similar mode diameters around 10 nm with total number
concentrations range of 7.0  105e1.0  106 #/cm3.
The generation mechanism of ultrafine particles from the
interaction between the tire and the road surface may be different
from that of tire wear or brake wear particles, which are produced
by mechanical abrasion. A plausible mechanism for the ultrafine
particle formation is the volatilization of tire-related organic ma-
terials or extender oils and subsequent condensation of materials
(Cadle and Williams, 1978). Dahl et al. (2006) explained that the oils
used as softening fillers had low vapor pressures and rapidly
condensed when cooled, if vaporized from the tire at the elevated
temperatures. The bitumen, which is a viscous hydrocarbon ma-
terial containing many chemical components (Jennings et al., 1992)
and is used as a binder in asphalt mixtures with the content of 5%
(Luhana et al., 2004), is also possible candidate for ultrafine particle
formation. In this study, it was assumed that there was no effect of
exhaust emission from the tailpipe on the ultrafine particle for-
mation because our sampling vehicle was gasoline-based and the
sampling inlet was located far away from the tailpipe.
Under same braking events on the proving ground, the particle
number size distributions of TPs sampled 90 mm above the road
surface had broader peak values (10 nme40 nm) (Fig. 3(c)) when
compared to TPs sampled 40 mm above the road surface (Fig. 3(a)).
In addition, the total number concentrations of TPs sampled 90 mm
above the road surface were 6 times higher than those sampled
40 mm above the road surface. This might be explained that a
nucleation burst of a lot of vapor evaporated from the interaction
between the tire and the road surface under braking conditions
continuously occurred by condensation and coagulation during the
transport to the sampling height 90 mm. Previous studies reported
that particle number size distribution changes rapidly with the
distance from the emission sources as nucleation mode particles
(<20 nm) grow fast by condensation or coagulation processes
forming Aitken (20e100 nm) mode particles (Charron and
Harrison, 2003; Zhu et al., 2002).
Fig. 4(a)e(c) show particle number size distributions of TPs
sampled 90 mm above the road surface for three cases of particle
growths during braking events at the proving ground on 13 August
2013. During the sampling day, rapid particle growths after the
 J. Kwak et al. / Atmospheric Environment 97 (2014) 195e205 199

Fig. 3. Particle number size distributions and total particle concentrations of TPs sampled 40 mm above the road surface at (a) the proving ground and (b) road simulator, and (c)
TPs sampled 90 mm above the road surface at the proving ground during braking events on 15 June 2012.

formation of ultrafine particles were observed. Note that in previ-
ous measurements (15 June 2012) under same braking events at the
proving ground, the growth event was weakly observed. This may
indicate that the TPs contain growth species and have a strong
dependence on ambient conditions. During the growth observation
day, both the temperature and relative humidity were higher when
compared to the other sampling day (15 June 2012). Several pre-
vious works have shown that meteorological parameters such as
temperature, humidity, and dilution strongly influence ultrafine
particle formation and growth (Abdul-Khalek et al., 1999; Easter
and Peters, 1994). In the study by Khalek et al. (2000), who
investigated nanoparticle growth during dilution and cooling of
diesel exhaust using a two-stage microdilution system, higher
diameter growth of ultrafine particles was observed at high tem-
perature and low humidity ratio.
When particle growth was observed during the braking events,
the growth rate (dDp/dt) based on the variation of geometric mean
diameters (GMD) as a function of time was calculated for the three
growth events (Fig. 5). For our study, the growth rate ranged from
1.9 to 2.1 nm/sec, which was much higher than typical values
observed in the ambient atmosphere (0.5e9 nm/h) (Kulmala et al.,
2004; Qian et al., 2007) and lower than those appeared in diesel
200 J. Kwak et al. / Atmospheric Environment 97 (2014) 195e205
Fig. 4. Particle number size distributions of TPs sampled 90 mm above the road surface for (a) 1st, (b) 2nd, and (c) 3rd particle growth during braking events at the proving ground
on 13 August 2013.
exhaust (2e24 nm/sec) (Khalek et al., 2000, 1999). In the study by
Kittelson et al. (2006), who characterized diesel exhaust aerosols in
on-road and laboratory measurements, and performed hygroscopic
measurements using tandem differential mobility analyzers
(TDMA), they reported that particle growth increased with
decreasing particle size and the smallest particles were enriched
with sulfuric acid. On the other hand, Khalek et al. (2000) estimated
that growth species present in the diesel exhaust to produce sig-
nificant particle growth were sulfuric acid and hydrocarbons that
comprised soluble organic fractions. General compounds in tire
tread are a variety of rubbers, vulcanizing agent, retardants, fillers,
reinforcing agents, softeners, activators, preservatives, anti-
oxidants, extender oils, etc. (Boulter, 2005). Among those com-
pounds, in our study, sulfur-containing (e.g., vulcanizing agent),
extender oils or hydrocarbon materials (e.g., bitumen in asphalt
pavements) might contribute to the particle growth. The above
results confirmed that the generation mechanism of ultrafine
particles especially during the harsh braking conditions is volatil-
ization of the organic materials, extender oils or hydrocarbons in
asphalt but not the wear of tire tread or road surface.
Particle number size distributions and total particle concentra-
tions of BPs measured at the proving ground and road simulator
during braking events on 15 June 2012 are shown in Fig. 6(a) and
(b), respectively. Note that both BPs were measured near the brake
pad (Fig. 1(3)). Under deceleration conditions, total particle
numbers of both BPs significantly increased and were higher than
those of TPs (Fig. 3(a)e(c)), suggesting that BPs have been shown to
be a one of the major contributors to ultrafine particles in an
ambient air. Both the BPs observed from the proving ground and
road simulator had same mode diameters at 10 nm. This finding is
in agreement with the study by Mathissen et al. (2011), who
measured airborne brake wear particles at the disk brake and re-
ported that the size distribution of 100 km/h full stop braking had a
mode diameter at 11 nm.
 J. Kwak et al. / Atmospheric Environment 97 (2014) 195e205 201

Fig. 5. Geometric mean diameter (GMD) of TPs sampled 90 mm above the pavement
surface when particle growth was observed during braking conditions on 13 August
2013: the growth rate (nm/sec) was calculated as the regression slope.

In our study, the temperature measured near the brake pad right
after braking events increased up to 500  C, which might result in
ultrafine particle formation from the thermal degradation of
organic materials or metals having low melting points contained in
brake pad (Garg et al., 2000). Kukutschova
et al. (2011) measured
airborne nano/micro-sized wear particles released from low-
metallic automotive brakes using a brake dynamometer and
observed significant release of nanoparticles when the average
temperature of the rotor reached 300  C. Similarly, in our study, the
thermo-oxidative degradation of organic materials or metals hav-
ing low melting points present in brake linings might lead to the
release of nanoparticles.

3.3. Cornering conditions

Cornering measurements were carried out only on the proving

ground because it was not possible to simulate the cornering
conditions in current road simulator study. We investigated the
effect of the height of sampling inlet on the size distributions or
number concentrations of TPs. Particle number size distributions
and total particle concentrations of TPs sampled 40 mm and 90 mm
above the road surface during cornering conditions on 15 June 2012
are shown in Fig. 7(a) and (b), respectively. The mode diameter of
TPs sampled 40 mm above the road surface was observed at
10e40 nm, while the size distribution of TPs sampled 90 mm above
the pavement had peak values at 10e20 nm. The extreme driving
conditions resulted in the increase of ultrafine particles compared
to constant speed driving.
The average total particle concentrations of TPs sampled 40 mm Fig. 6. Particle number size distributions and total particle concentrations of BPs at (a)
and 90 mm above the road surface were 1.8  106 ± 2.2  106 #/cm3 the proving ground and (b) road simulator during braking events on 15 June 2012.
and 3.8  104 ± 1.0  104 #/cm3, respectively. In contrast to braking
events, higher number concentrations of TPs sampled 40 mm above were forced by further increase of the velocity, which resulted in
the road surface were observed than those obtained 90 mm above enhanced peak particle concentrations up to 3.5  106 #/cm3.
the pavement. It might be explained that the ultrafine particle for- Despite different mobile sampling vehicle and measurement setup,
mation was completed before the transport to the sampling height the particle size distribution and number concentrations of TPs
of 40 mm and the dilution by surrounding air mainly occurred above observed 40 mm above the road surface in our study showed similar
the sampling height of 40 mm without further nucleation and results with those measured by Mathissen et al. (2011).
condensation processes (Kwak et al., 2013b). Mathissen et al.
(2011) also observed enhanced ultrafine particles with the mode 3.4. Morphological and elemental analysis of TPs
diameter between 30 and 60 nm during cornering tests on a curve
diameter of 48 m at a vehicle speed of 48 km/h using a mobile We conducted morphological and elemental analysis for 100 nm
sampling vehicle. They explained that more extreme conditions mobility-classified ultrafine particles. The TPs sampled 90 mm
202 J. Kwak et al. / Atmospheric Environment 97 (2014) 195e205
Fig. 7. Particle number size distributions and total particle concentrations of TPs
sampled (a) 40 mm and (b) 90 mm above the road surface during cornering conditions
on 15 June 2012.
above the pavement surface from on-road driving and road simu-
lator measurements during braking events were classified into
several distinct types according to their morphology and elemental
composition. The TEM/EDS analyses for on-road measurements are
shown in Fig. 8(a)e(d) and for road simulator study in Fig. 9(a) and
(b).

The particles shown in Fig. 8(a) was rapidly evaporated under
high vacuum and strong electron beam intensity in the TEM,
indicating that they might consist of volatile materials (e.g.,
volatile organic carbon, nitrate, or sulfate). This finding is
consistent with previous studies by Smith et al. (2012), who
reported that sulfur-containing particles were electron beam
sensitive and damaged easily, resulting in rapid change in
morphology and the appearance of moving pores within a
particle. In the EDS analysis, the particles mainly included C, O, S,
Si, and Cu. According to previous research (Kirchner et al., 2009),
however, Si signal was found to be an artifact from the EDS
detector and the TEM sample always showed a Cu signal in the
EDS spectrum due to the copper grid used in this study. If these
particles were generated from tires, these particles might result
from S-containing vulcanizer or anti-oxidants. Or the bitumen
in asphalt pavement also contains significant amount of sulfur
and silica (Thorpe and Harrison, 2008), thus these particles
could be from bitumen in asphalt pavement.

Amorphous carbonaceous aggregates containing several metals
were observed from both on-road driving (Fig. 8(b)) and road
simulator measurements (Fig. 9(a)). The inclusions of Fe, Pd, Ca,
K, and Ti found during on-road measurements might be resulted
from brake wear, fuel additives, engine oil, or previously
deposited materials on the proving ground. Palladium (Pd) is a
representative element used as three-way catalysts for gasoline
engine exhaust reduction (Wang et al., 2011). The brake lining
used in this study is an NAO (non-asbestos organic) type lining,
which are descendants of asbestos formulations but substituted
potassium titanate fibers (Sanders et al., 2003). Ti could be an
important marker of wear particles from NAO brakes. The TEM/
EDS analysis for the road simulator measurements did not show
Pd, Ca, K, and Ti signals since there was no effect of exhaust
emissions and deposited materials during the laboratory ex-
periments. In our study, the collected ultrafine particles during
road simulator measurements were not enough to analyze the
particles from various sources.

Near-spherical agglomerates having 20 nm primary particles
and consisting of C, O, and S were observed as shown in Fig. 8(c).
Their morphologies were similar to those of diesel exhaust
(soot), but they didn't come from diesel soot because they were
found to have paracrystalline structure having short and me-
dium range ordering in their lattice from the examination of
selected area electron diffraction patterns. This morphology
agrees with previous study by Dahl et al. (2006), who explained
that the agglomerates originated from the carbon black rein-
forcing filler of tires. However, there are strong covalent bonds
between carbon black and the rubber matrix, and thus is un-
likely that individual particles of carbon black could be released
from the rubber matrix and therefore the origin of these parti-
cles might not from carbon black reinforcing filer. These parti-
cles were not evaporated nor volatilized by heat and found to
have paracrystalline structure and graphene layer, thus it might
be a black carbon although the origin was not clear.

A number of spotted particles less than 10 nm in size were
observed from on-road driving (Fig. 8(d)) and road simulator
measurements (Fig. 9(b)). This observation agrees well with the
mode diameter of the particle number size distributions of TPs
during braking events (Fig. 3). The EDS and selected area elec-
tron diffraction analyses revealed that the spotted particles
consisting of C, O, and S were in crystalline forms. From the
results, it is likely that the 10 nm-sized particles may be resulted
from graphite-like materials.
However, uncertainties still remain in the identification of
possible emission source of ultrafine particles especially under
braking events because TPs, BPs, and pavement wear particles are
simultaneously emitted under extreme driving conditions, and
Fig. 8. Morphology and elemental analysis of TPs sampled 90 mm above the pavement surface during on-road measurements under braking events. The analyses were made with
TEM/EDS method.
204 J. Kwak et al. / Atmospheric Environment 97 (2014) 195e205
Fig. 9. Morphology and elemental analysis of TPs sampled 90 mm above the pavement surface during road simulator experiments under braking events. The analyses were made
with TEM/EDS method.
they may be mixed and sampled together into the sampling inlet.
Sulfur signals shown in TEM images can be attributed to ZnS from
TPs, or Sb2S3 and BaSO4 from BPs. In addition, semi-volatile parti-
cles are likely to vaporize in the high vacuum environment of the
TEM and not be observed (Smith et al., 2012). Zinc could be a dis-
tinguishing elemental marker for tire wear particles, however all
the EDS spectra didn't show zinc element, thus it was hard to
confirm that the particles were generated from tires. TPs are the
mixture of various particles originated from tire, brake, road sur-
face, road dust, and atmospheric composition depositions, etc. After
the enough TEM/EDS analyses, source apportionment could be
possible.
4. Conclusions
In this study, we applied a mobile sampling vehicle for on-road
driving and road simulator measurements to investigate the
physical and chemical characteristics of ultrafine particles emitted
from non-exhaust sources under different driving conditions. Our
findings indicate that the ultrafine particle concentrations emitted
during braking and cornering conditions significantly increased
compared to under constant speed driving. Under braking events,
broader mode diameter and higher number concentration of TPs
sampled 90 mm above the road surface was observed compared to
those obtained 40 mm above the road surface. In addition, the
particle growth event observed on 13 August 2013 identified the
possible growth species present in TPs or BPs. A plausible mecha-
nism for the ultrafine particle formation under harsh braking
conditions is the volatilization of tire-related organic materials,
extender oils, or bitumen from the pavement and subsequent
condensation of materials.
The TEM/EDS studies of TPs sampled from on-road driving and
road simulator measurements during braking events identified
several distinct types of particle such as sulfur-containing mate-
rials, anti-oxidants, and carbon black which can be contained in
TPs, and/or graphite, solid lubricant (Sb2S3), and BaSO4 which are
mainly present in BPs. However, all the EDS spectra didn't show
Zn element which could be a distinguishing elemental marker
for tire wear particles, thus it couldn't say that it was from tires.
Further research would be required as to whether the exact
emission source of ultrafine particles is TPs, BPs or asphalt
pavement.
Acknowledgments
The present study was supported by the Center for Environ-
mentally Friendly Vehicles (CEFV) under the project “Development
of the eco-friendly tire for reduction of carbon dioxide and tire wear
particles” through the Ministry of Environment (ME, Republic of
Korea).
 J. Kwak et al. / Atmospheric Environment 97 (2014) 195e205 205

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