Science of the Total Environment 408 (2010) 652–659

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Science of the Total Environment

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s c i t o t e n v

Physical and chemical characterization of tire-related particles: Comparison of particles

generated using different methodologies
Marisa L. Kreider a,⁎, Julie M. Panko a, Britt L. McAtee a, Leonard I. Sweet a, Brent L. Finley b
a
ChemRisk, Inc., 20 Stanwix Street, Suite 505, Pittsburgh, PA 15222, USA
b
ChemRisk, Inc., 25 Jessie Street, Suite 1800, San Francisco, CA 94105, USA

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

Article history: The purpose of this study was to characterize the physical and chemical properties of particles generated
Received 30 April 2009 from the interaction of tires and road surfaces. Morphology, size distribution, and chemical composition
Received in revised form 2 October 2009 were compared between particles generated using different methods, including on-road collection,
Accepted 7 October 2009
laboratory generation under simulated driving conditions, and cryogenic breaking of tread rubber. Both
Available online 6 November 2009
on-road collected and laboratory generated particles exhibited the elongated shape typical of tire wear
particles, whereas tread particles were more angular. Despite similar morphology for the on-road collected
Keywords:
Tire
and the laboratory generated particles, the former were smaller on average. It is not clear at this stage if the
Tire wear particles difference is significant to the physical and chemical behavior of the particles. The chemical composition of
Road dust the particles differed, with on-road generated particles containing chemical contributions from sources other
Size distribution than tires, such as pavement or particulates generated from other traffic-related sources. Understanding
Chemical composition the differences between these particles is essential in apportioning contaminant contributions to the
Zinc environment between tires, roadways, and other sources, and evaluating the representativeness of toxicity
studies using different types of particulate generated.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction
Recent interest in the effects of particulate matter associated
with road traffic on local environments and human health has spurred
research towards defining and characterizing the sources of these
particles. The use of tires has been implicated as a source of metals and
other chemicals in soil, air, and urban runoff, although there has yet
to be a consensus on the definition and characterization of particles
generated from tire use (Davis et al., 2001; Fergusson and Kim, 1991;
Fergusson and Ryan, 1984; Rogge et al., 1993; Sadiq et al., 1989;
Smolders and Degryse, 2002). While there is a clear understanding
of tire tread composition, the characteristics of particles generated
during the use of the tire are not well understood. The manufacturing
of a tire is a complex process, requiring use of a wide variety of
chemicals, fillers, and polymers. While the specific recipes used in tire
manufacturing are dependent upon the desired characteristics of the
tire, the primary components of tire tread remain consistent. Both
unreactive (polymers, fillers, oils, waxes, resins, processing aids, and
antioxidants) and reactive chemicals (sulfur compounds, accelerators
and retarders, adhesives, and activators) are used in the compounding
of tire tread. Most reactive chemicals are consumed during tire
manufacturing, primarily in the vulcanization and curing process
(Lawrence Livermore National Laboratory, 1996; U.S. EPA, 1997).
⁎ Corresponding author. Tel.: +1 412 281 6900x1027; fax: +1 412 281 6999.
E-mail address: mkreider@chemrisk.com (M.L. Kreider).
Tire wear debris has been defined as particles generated by the
rolling shear of tread against a surface (Rogge et al., 1993). However,
as the tire is used, interaction with the road is thought to alter the
chemical composition and characteristics of the particles generated
during contact with paved surfaces when compared to original tread
through either heat and friction or via incorporation of material from
the road surface (Adachi and Tainosho, 2004; Williams and Cadle,
1978). Several studies have characterized particles from tires using
rolling resistance machines or other methods (Cadle and Williams,
1978; Camatini et al., 2001; Davis et al., 2001; Ozaki et al., 2004; Rogge
et al., 1993; Sadiq et al., 1989; Williams and Cadle, 1978). However, in
an on-road scenario, as the tire passes over the road, particles from the
tread combine with existing road dust and minerals from the
pavement to produce a unique entity. Adachi and Tainosho (2004)
demonstrated that rubber-containing particles in road dust are
incorporated with metals from alternative contributing traffic-related
sources (i.e. paint and brake dust). Therefore, the characteristics of
particles generated during on-road use of tires are likely to differ
from original tread as well as those particles generated on laboratory
rolling machines.
To date, little research has been done on tire wear particles
generated during realistic driving conditions. Researchers who have
studied tire debris and tread loss have reported wide size distribu-
tions ranging from 5 μm to more than 300 μm (Cadle and Williams,
1978; Dannis, 1974). Recent studies have been conducted to
understand the size distribution of the airborne fraction of tire wear

0048-9697/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2009.10.016
 M.L. Kreider et al. / Science of the Total Environment 408 (2010) 652–659
particles (TWP), and the results indicate that these distributions
vary with tire type (non-studded or studded) and pavement type
(Gustafsson et al., 2008). Chemical characterizations of tire wear
debris or tire particles have primarily addressed metallic content,
although studies of tire particle toxicity in aquatic species and human
cell lines have implicated organic constituents of tires (Adachi and
Tainosho, 2004; Davis et al., 2001; Gualtieri et al., 2008; Ozaki et al.,
2004; Rogge et al., 1993; Sadiq et al., 1989; Wik, 2007; Zheng et al.,
2002). In addition, the contribution of tires to polycyclic aromatic
hydrocarbons (PAHs) in road dust has also been discussed in recent
literature, with contrasting results (KEMI, 2003; Macias-Zamora et al.,
2002; Rogge et al., 1993; Takada et al., 1990; Zakaria et al., 2002). This
culminated in the European regulation requiring the discontinua-
tion of the use of high aromatic oils (which contain PAHs) in the
manufacture of tires starting in 2010 (European Commission, 2005).
Although only limited attention has been paid to the character-
ization of tire wear particles, several research groups have been
committed to investigating the toxicity of tire debris. TWP has been
implicated as an aquatic toxicant based on the potential to induce
endocrine disruption, acute lethality, and teratogenicity (Gualtieri
et al., 2005a; Mantecca et al., 2007; Wik, 2007; Wik and Dave, 2005,
2006; Zheng et al., 2002). In addition, a few studies have evaluated
the potential for airborne tire particles to induce in vitro or in vivo
pulmonary toxicity, suggesting that inhalation of TWP represents a
health risk to humans (Gualtieri et al., 2008, 2005b; Mantecca, 2009).
In these various studies, the representativeness of the test particles as
those generated under realistic driving conditions is questionable.
Further, limited information regarding the characteristics of the
particles is available.
The purpose of this study was to characterize the physical and
chemical properties of particles from tires using different methodol-
ogies of particulate generation. Until recently, particles generated
from tires could not be effectively collected under representative
driving conditions, either on-road or in laboratories. However, the
methods for collection of both on-road and laboratory generated
particles developed by the authors allowed for collection of particles
that are similar to those generated during realistic driving conditions
(Supplementary materials). In order to understand the potential
environmental contributions and toxicity from particles derived from
tires, it is necessary to characterize the physical and chemical
properties of these particles. While the characterization methods
presented here may not allow for an understanding of crosslinking or
polymeric structure changes in the rubber compound itself, gross
physical and chemical characteristics of the particles, including
impact of the road surfaces and the environment on the particles,
were investigated. Comparisons were made between roadway
particles (RP), collected during outdoor driving which contain
contributions from tires as well as other sources (i.e., fuel, brakes,
pavement, atmospheric deposition, etc.); TWP, collected on a
simulated laboratory driving course; and tread particles (TP),
cryogenically ground from pieces of unused tread. A diagram
delineating the relationships between these three particle types can
be seen in Fig. 1. By making such comparisons, it will be possible to
more accurately determine the contribution of tires to RP, and sub-
sequently assess the potential for environmental or health impacts
as a result of this contribution.
2. Methods
2.1. Generation and collection of roadway particles (RP), tire wear
particles (TWP), and tread particles (TP)
On-road collection of RP was conducted as described in the
Supplementary materials. Briefly, Michelin Engineering Services
designed two on-vehicle TWP collecting devices, one for a passenger
car (BMW 528i, Model year 1999) and one for a truck (MAN 1846
653
Standard 19 Ton). Each collection device consisted of an aspiration
system attached to the rear left tire hub very close to the tire. The
aspiration systems included a slot type capture hood, connected to
a cyclonic cup which retained particles in the size fraction of 0.3–
100 µm. Verification of particle retention in the system was conducted
prior to the beginning of RP collection, using kaolin clay with a known
particle size distribution. A description of this study can be found in
the Supplementary materials. The premise of the collection system is
similar to that of other mobile systems that measured particles from
behind the tire during real driving (Hussein et al., 2008; Pirjola
et al., 2004). However, while those systems aimed to take real-time
measurements of airborne particle generation, our system was
equipped with a collection device capable of collecting the fraction
that is normally deposited on the road surface (Hussein et al., 2008;
Pirjola et al., 2004).
Two driving circuits in Clermont Ferrand, France were used to
represent typical driving commutes in Europe, North America and
Japan. For passenger cars, the circuit consisted of 2/3 urban road and
1/3 motorway, and for trucks, the circuit was comprised of 1/3 urban
road and 2/3 motorway. Although pavement types may differ
regionally (based on local supply of aggregate, weather conditions,
etc.), asphalt-based pavements are the predominant road surfaces in
the United States and Europe (EAPA, 2007; FHWA, 2006). In fact, in
the U.S., 94% of road surfaces are asphalt-based (FHWA, 2006). In
order to maintain the most consistent pavement type possible in the
driving circuit and to use a driving circuit that is representative of
average driving conditions, all roads used to generate the particles
were asphalt-based.
Three typical tires were used during the collection of RP including
two passenger tires, one that contained silica as the filler (Michelin
Pilot Primacy 225/55/R16 95W) and one that contained carbon black
as the filler (Goodyear SAVA INTENSA 235/45/R17). Because there is
less variation in truck tires, only one type of tire was used for the truck
collection (Michelin DA2 + 315/80 R22.5). Particles collected in the
cyclone were removed by tapping the outside of the container and
scraping along the inside surfaces with a stainless steel mini-scoopula.
Collections from each tire type were carefully combined to generate
a representative composite and sieved at 150 μm to remove large
particles, such as rocks or other debris.
TWP were collected at a road simulator laboratory located with-
in the Bundesanstalt für Straßenwesen (BASt), the German Federal
Fig. 1. Schematic representing the contributors to particles evaluated in this study.
Roadway particles (RP), tire wear particles (TWP), and tread particles (TP).
654 M.L. Kreider et al. / Science of the Total Environment 408 (2010) 652–659
Highway Research Institute, as described in the Supplementary
materials. Briefly, the BASt operates an interior drum testing system
(IPS) that is used primarily to test skid resistance of various road
pavements, including wet road surfaces. The IPS contains actual road
pavement and is electronically programmable to mimic a variety of
driving conditions by varying speed, temperature, load, acceleration,
braking and steering. For the TWP collection, the pavement consisted
of a standardized asphalt concrete with 6.1% proportion of bitumen
(B50/70) according to ISO 10844. An asphalt-based pavement was
selected to most closely approximate the pavement types from the
on-road driving circuit and to represent typical European road
surfaces. Along with driving parameters (e.g., speed, acceleration,
braking, turning, etc.), surface texture is an important predictor of tire
wear or frictional force between tire and pavement (Dahl et al., 2006;
Gunaratne et al., 2000; Gustafsson et al., 2008). Measurements of the
pavement textures used at the BASt were made and found to be
similar to that of European roads. However, because the laboratory
pavement is not subjected to weathering or other natural conditions,
a polishing effect can occur such that the surface becomes smoother.
The comparison of the BASt pavement to standard German pavements
or other laboratory tread testing materials is shown in Fig. 6 in the
Supplementary materials.
The TWP collection device was designed similar to that used for
the RP collections. Both summer and winter silica based tires
(Michelin Pilot Primacy 225/55 R16 95W and Pirelli Sottozero 225/
55 R16 95W M + S) and a summer carbon black tire (Bridgestone
Potenza RE 88 205/65 R15 94W) were used to generate the TWP.
Because truck tires could not be used in the road simulator laboratory
at BASt, TWP from truck tires were not included in the composite.
However, preliminary studies (not shown) indicated that the size
distribution and general composition of truck tire tread were not
substantially different from the passenger tires so as to prevent
comparison between the RP and TWP. The dynamic driving course
used during the collection was designed to replicate a combination of
city and highway driving and included both acceleration, decelera-
tion, and turning. The course, which was repeated until collection was
completed, was 183 km; speeds varied between 30 and 150 km/h, and
acceleration/deceleration rates did not exceed 2 m/s2. Static driving
conditions included a wheel load of 4248 N and a camber angle of
−1.6°. Particles from each tire were combined to form a single
composite for analysis, and as with the RP, the composite of TWP
was also sieved at 150 µm.
TP were generated using shavings of the tread from the same tires
as used during the TWP collection. These pieces of tread were crushed
under cryogenic conditions and sieved to 180 µm. Based on the cryo-
genic methodology used to generate the particles, sieving at 150 µm,
was not feasible for producing the quantity of ground TP the study
required.
2.2. Morphology and particle size analysis
Qualitative morphology of RP, TWP, and TP was determined using
scanning electron microscopy (SEM). Quantitative morphology of RP
and TWP was determined using transmission optical microscopy
(Malvern Morphologi G3 with Automated Particle Characterization
System) based on shape parameters. Elongation was quantified by
the aspect ratio (ratio of length to width), and is unaffected by sur-
face roughness. Circularity is a measure of the closeness to a perfect
circle, and is sensitive to changes in form and surface roughness The
distribution of the values for both of these parameters was quantified
for RP and TWP. Particle size distributions for RP and TWP were
determined using transmission optical microscopy and laser diffrac-
tion. The transmission optical microscope was a Malvern Morphologi
G3 with Automated Particle Characterization System, which is capable
of quantifying size distribution by both volume of particles and
number of particles. Laser diffraction was conducted according to ISO
standard 13320-1 (Particle size analysis — Laser diffraction method).
Size analysis was not performed for the cryogenically ground TP, as
they are not representative of particles generated under conditions
related to the use of the tire.
2.3. Chemical analysis of particles
General composition of each RP, TWP, and TP composite was
determined according to NFT 46-047 standard (Rubber and rubber
products — Determination of composition of vulcanizates and uncured
compounds by thermogravimetry) and NFT 46-100 (Rubber —
Determination of solvent extract). This allowed for identification
of composition of the particles by general chemical class, including
plasticizers and extractible matters; polymers; carbon blacks; and
inorganic ingredients in the tire tread (dehydrated or decomposed) and
minerals from the road. Following thermogravimetric analysis for
general composition, the ash from each composite was analyzed
according to ASTM D 1971-02, using a Spectro FTP-08 ICP-OES
instrument according to the manufacturer's instructions to identify
and quantify metal content of the particles. In addition to metallic
analysis of the ash, the particles were analyzed for specific elements
known to be used during compounding of the tread, including silicon,
sulfur, and zinc, using NF EN 13656 (Characterization of waste —
Microwave assisted digestion with hydrofluoric [HF], nitric [NO3], and
hydrochloric [HCl] acid mixture for subsequent determination of
elements) and ISO 11885 (Water quality — determination of 33
elements by inductively coupled plasma atomic emission spectroscopy).
Polycyclic aromatic hydrocarbons (PAHs) were quantified according to
XP X 33-012 (Characterization of sludges — determination of polycyclic
aromatic hydrocarbons [PAH] and polychlorinated biphenyls [PCB] by
gas chromatography coupled with 2D mass spectrometry [GC/MS/MS]).
3. Results
3.1. Morphology
Images taken with the scanning electron microscope (Fig. 2A)
indicate that RP are elongated in shape and contain incrustations
of minerals from the road surface (Fig. 2B). TWP maintain a similar
shape and mineral inclusion (Fig. 2C, D). In comparison, cryogenically
generated TP are more jagged in shape (data not shown). Quantitative
analysis of particle morphology through determination of particle
circularity and elongation metrics indicates that the particle shape
of the RP and TWP is nearly identical (Fig. 3). The modes for the
distribution of circularity measures of the particles are 0.84 and
0.83 for RP and TWP, respectively. For aspect ratio, the values for the
modes of the distribution are equivalently similar, with values of 0.63
and 0.64 for RP and TWP, respectively. These results indicate that
using both observational and quantifiable methods, RP and TWP have
similar morphology, while TP differs.
3.2. Size distribution
Size distributions by volume of particles for RP and TWP can be
seen in Fig. 4. The size distribution by volume of particles for RP, as
determined by laser diffraction, is unimodal, spanning from 4 µm to
280 µm with the mode centered at approximately 50 µm (Fig. 4A).
Using the same methodology, the size distribution by volume of
particles for the TWP was also unimodal ranging from 5 µm to
220 µm, with a mode centered at approximately 75 µm (Fig. 4B). The
size distributions by volume as determined by transmission optical
microscopy were similar to the laser diffraction method. For RP, the
distribution ranged from 4 μm to 265 μm with a mode at 50 μm; for
TWP, the distribution ranged from 4 μm to 350 μm, with a mode at
100 μm (Fig. 4C and D). Based on these size distributions, RP are
smaller on average than TWP. When considering size distribution by
 M.L. Kreider et al. / Science of the Total Environment 408 (2010) 652–659
Fig. 2. Scanning electron microscope images of RP (A, B) and TWP (C, D). Scales are located below the photos. Mineral incrustations are evident in the photos of greater
magnification (B, D).
number of particles (Fig. 5), however, the pattern of distribution is
different between RP and TWP. The RP maintains a size distribution
that is unimodal by number of particles, with a range from 4 μm
to 265 μm and a mode of approximately 25 μm (Fig. 5A). The TWP,
however, exhibits a bimodal distribution, with a range from 4 μm to
350 μm with peaks at approximately 5 μm and 25 μm (Fig. 5B).
3.3. Chemical composition
General chemical composition of RP, TWP, and TP as determined
by thermogravimetric analysis is presented in Table 1. RP and TWP
had similar compositions, although the RP was comprised of slightly
more oils, plasticizers and polymers whereas TWP had a higher
mineral content. TP had more polymer and less mineral content than
both the RP and TWP. The mineral content of the RP and TWP is
expected to include that from the fillers used in the tread compounds,
the minerals embedded into the particles from the pavement and road
dust during rolling, and “free” minerals from the pavement.
Results of the analysis of the metallic content of the three types of
particles are presented in Table 2. The metals detected in the highest
quantities in RP and TWP, aluminum and silicon, are also found in
high quantities in asphalt (Legret et al. 2005). Because these metals
are found in substantially smaller quantities in TP, they likely
originate primarily from the pavement surface, as opposed to the
tire. Other metals (also likely components of pavement or present on
the road surfaces from other sources), such as iron, sodium, calcium,
potassium, and magnesium, are also found in elevated levels in RP and
655
TWP when compared to TP. Detailed composition information for the
pavement surfaces on which the RP or TWP were collected was not
available; therefore, it is difficult to make conclusions about the
sources of these metals in the RP. However, in the TWP, only the
pavement or the tire can contribute to the particulate, therefore those
metals not detected in the TP that are present in high quantities in the
TWP must originate from the pavement. Further, metals present in
appreciably larger quantities in RP than TWP likely originate from
non-pavement sources on the road surface.
Zinc, a metal used in rubber compounding in the form of ZnO,
is found in TP at approximately 9000 ppm. This is consistent with
previous studies evaluating the concentration of zinc in tire tread
reporting a range of findings from approximately 3000 to 10,000 ppm
(Davis et al., 2001; Legret and Pagotto, 1999; Pierson and Brachaczek,
1974; Waddell and Evans, 1996), with an expected value of ap-
proximately 10,000 ppm (1%) based on common formulations (Stern,
1967; U.S. EPA, 1997). Based on the results from this study, the
concentration of zinc in the corresponding TP is approximately two
and three times higher than found in RP and TWP, respectively. These
results indicate that tread rubber is likely to be a major, although not
sole contributor of zinc in the RP and TWP.
While tires have been proposed as the major contributor of zinc in
road dust, which typically contains anywhere from 300 to 2600 ppm
zinc, and environmental media brake dust, other traffic-related mate-
rials, such as metallic barriers, automobile exhaust, and cement also
contain zinc and may contribute to zinc content in the environment
(Fergusson and Ryan, 1984; Ozaki et al., 2004; Pagotto et al., 2001;
656 M.L. Kreider et al. / Science of the Total Environment 408 (2010) 652–659

Fig. 3. Quantitative measures of morphology, including circularity (A, B) and elongation (C, D) for RP (A, C) and TWP (B, D). The distribution is smoothed over 11 data points for both
circularity and elongation. Each graph includes the probability distribution and the cumulative distribution for each measure. HS — High sensitivity.

Sadiq et al., 1989; Wang et al., 2006; Warren and Birch, 1987). levels of zinc in the particulate mixture. Further, as there is evidence
However, the concentration of zinc in RP is approximately 33% higher that TWP contain more mineral content (see Table 1) than RP, the zinc
than in TWP, indicating that additional contributors of zinc may be in the TWP may have a greater dilution by pavement material than
present in the on-road collection environment, thus influencing the in the RP. Although the RP and TWP were generated on different

Fig. 4. Particle size distribution determined by volume of particles according to laser diffraction (A, B) and transmission optical microscopy (C, D) for RP (A, C) and TWP (B, D). The
distributions are smoothed over 30 data points for the size distribution as determined by transmission optical microscopy. Figures (A) and (B) include repeated measures of the same
distribution. Figures (C) and (D) include both the probability distribution and the cumulative distribution for each measure.
 M.L. Kreider et al. / Science of the Total Environment 408 (2010) 652–659 657

Table 2
Analysis of metallic content of particles.

Metal RP TWP TP

Used in tire manufacturing

Zinc 4000 3000 9000
Silicon 86,000 87,000 54,000
Sulfur 9000 5000 12,000

Other metals
Aluminum 33,900 28,200 470
Antimony N.D. 130 76.5
Arsenic 122 N.D. N.D.
Beryllium N.D. N.D. N.D.
Bismuth N.D. N.D. 86.8
Boron 53.7 N.D. N.D.
Cadmium N.D. N.D. N.D.
Calcium 27,600 65,300 1010
Chromium N.D. N.D. N.D.
Cobalt N.D. N.D. N.D.
Copper 188 634 21.5
Iron 33,000 27,700 224
Lead 49.7 N.D. N.D.
Magnesium 10,800 14,500 65.8
Manganese 509 607 N.D.
Nickel 40.8 52.6 N.D.
Potassium 8840 5810 242
Selenium N.D. N.D. N.D.
Silver N.D. N.D. N.D.
Sodium 7140 4750 N.D.
Titanium 2810 1390 29.9
Vanadium 60.6 49.6 N.D.

Values are expressed in parts per million (ppm) of particle mixture. Separate metals
Fig. 5. Particle size distribution by number of particles for RP (A) and TWP (B) as determined
analyses were conducted for elements used in tire manufacturing (e.g. zinc, sulfur, and
by transmission optical microscopy. The distributions are smoothed over 30 data points.
silicon; NF EN 13656) and those not generally associated with tires (ICP-OES analysis of
Figure (B) includes the probability distribution and the cumulative distribution.
ash). TP are from the tread of the tires used to generate the TWP. N.D. = Not detected.
Detection limits vary by sample type based on ash content of sample. Average detection
pavements of unknown zinc content, it is not anticipated that limits (ppm) for metals not detected: Sb — 44.4; As — 64.5; Be — 1.08; Bi — 32.3; B —
68.2; Cd — 4.99; Cr — 245; Co — 163; Cu — 107; Pb — 13.9; Se — 171; Ag — 117; Na —
zinc content in the RP or TWP will be appreciably affected by the
42.2; V — 85.5.
pavement. Legret et al. (2005) detected zinc at 40 ppm in a sample
of asphalt-based pavement. Although the representativeness of this
pavement is unknown, this data suggests that pavement contains
zinc at far lower concentrations than in RP or TWP (approximately include natural sources, asphalt, automobile exhausts, and fuel
4000 ppm and 3000 ppm, respectively). combustion products (including coal) (Liu et al., 2007; Macias-
Silicon, like zinc, is a metal found in a high percentage in some Zamora et al., 2002; Takada et al., 1990; Zakaria et al., 2002). Analysis
tire formulations, as a result of the use of amorphous silica (silicon of PAH concentrations in TWP also reinforces that there is likely little
dioxide) in tire filler materials. Silicon, however, was detected at contribution from tires to the PAHs in RP (PAHs in RP are significantly
higher quantities in the RP and TWP, when compared to the TP. While
amorphous silica is used as a filler in some tires, silicon is also found
in cement and other road surfaces, and is the second most abundant Table 3
element in the Earth's crust. Therefore, the increased presence of Analysis of polycyclic aromatic hydrocarbon (PAH) content of particles.
silicon in RP and TWP is likely a result of its presence in the pavement Chemical RP TWP TP
or environmental dusts from sand or soil.
Acenaphthene 4.08 0.04 0.13
Analysis of PAHs in RP and TP also indicates a significant contri- Naphthalene 6.1 0.2 1.18
bution of non-tire sources to the RP. For all PAHs analyzed except Phenantherene 53.4 1.66 1.21
acenaphthalene, RP contained significantly higher quantities of PAHs Pyrene 54.84 4.77 0.06
when compared to TP (p < 0.005) (Table 3). In fact, the total PAH Acenaphthalene 0.14 0.15 1.24
Anthracene 7.36 0.1 0.11
content of the TP represented only 5% of the total PAH content of
Benzo(a)Anthracene 38.65 0.18 2.87
the RP. This corresponds well with previous studies estimating a low Benzo(a)pyrene 12.51 0.28 N.D.
contribution of tires to total PAHs in road dust and environmental Benzo(b)fluoranthene 7.4 0.37 0.92
media (Macias-Zamora et al., 2002; Takada et al., 1990; Zakaria et al., Benzo(g,h,i)perylene 4.04 3.22 1.77
2002). Proposed alternative sources of PAHs in the environment Benzo(k)fluoranthene 7.4 0.02 0.92
Chrysene 17.72 0.36 2.95
Dibenzo(a,h)anthracene 2.56 0.1 0.87
Fluoranthene 82.13 0.98 1.62
Table 1 Fluorene 1.76 0.07 0.25
General composition analysis of particles as determined by thermogravimetric analysis. Indeno-1,2,3(c,d)pyrene 5.36 0.21 N.D.
Total 305.45 12.71 16.1
Chemical family RP TWP TP
Values are expressed in parts per million (ppm) of particle mixture. Total PAHs
Plasticizers and oils 13 10 19
represent the sum of the individual PAHs that were analyzed. This list is not an
Polymers 23 16 46
exhaustive list of PAHs, but represents the most common PAHs found in the
Carbon blacks 11 13 19
environment and includes PAHs considered by IARC to be carcinogenic. N.D. = Not
Minerals 53 61 16
Detected. Detection limits for non-detect PAHs: benzo(a)pyrene — 0.01; indeno-1,2,3
Values are expressed in percent by mass. (c,d)pyrene — 0.01.
658 M.L. Kreider et al. / Science of the Total Environment 408 (2010) 652–659
higher than in TWP [p < 0.005]), as the total PAH level in TWP is
approximately 4% of that found in RP. The profile of PAHs differs
somewhat between TP and TWP, which may be explained by the
addition of the pavement component to TWP, as asphalt bitumen may
contain PAHs (Legret et al., 2005; Mahler et al., 2004).
4. Discussion
Because several recent studies have attempted to identify and
apportion contributions to atmospheric and deposited particulate
from traffic-related sources, the purpose of this work was to charac-
terize particulate generated as a tire passes over a roadway. In order
to accomplish this, physical and chemical characterizations were
determined for RP, which may contain mineral content from
pavement as well as embedded metals or other chemicals from
contribution of other traffic or environmental sources; TWP, which
were produced under simulated driving conditions on laboratory
road surfaces devoid of contributions from other traffic-related
sources (i.e. brake dust, diesel exhaust, etc.); and TP, which were
cryogenically ground from pieces of tread rubber and therefore do
not contain contributions from road surfaces or from other traffic or
environmental sources.
Based on visual inspection and quantitative measures of shape, the
morphology of the RP and TWP generated in this study is similar to that
reported in previous literature, with an elongated “sausage-like” shape
(Adachi and Tainosho, 2004; Cadle and Williams, 1978; Dannis, 1974;
Padovan et al., 1999; Williams and Cadle, 1978). However, alternative
methods for producing TWP in the laboratory, including a steel brush,
grit paper, or other abrasive media, while producing similarly shaped
particles, were not able to replicate driving conditions, and thus may
not generate a relevant size distribution. Furthermore, these methods
sometimes require the use of talc or other anti-smear agents which can
become incorporated into the particulate mixture making it difficult to
isolate the tire-related particles for biological assays (Camatini et al.,
2001). The shape of the RP and TWP is very different from that seen in
the cryogenically ground TP, which have sharper, more defined edges.
Morphology is an important consideration when evaluating toxicity of
particulate, especially through inhalation. Previous work with asbestos
and silica has demonstrated that the toxic potency of a particle can vary
with particle morphology (Stanton et al., 1981, 1977; Warheit et al.,
1995). Therefore, the use of cryogenically broken TP as a surrogate for
TWP in respiratory toxicity studies is inappropriate, and conclusions
derived from such experiments may be incorrect.
Using both methods for determining size distribution, the RP appear
somewhat smaller than the TWP on average, although this difference is
small. The two methods for determining size distribution, transmission
optical microscopy and laser diffraction, offer different approaches for
determining size distribution of the particles; based on these differ-
ences, these two methods may result in somewhat different reported
size distributions for particles. The transmission optical microscopy
method detected a larger range of particle sizes and as a result a larger
average particle size than the laser diffraction method. The laser
diffraction method usually assumes a spherical particle shape, while the
transmission optical microscopy method estimates the circle equivalent
diameter of the particles based on area of the particle. Regardless of
method, however, both the RP and TWP demonstrate a unimodal
distribution of particle size by volume of particles, with TWP maintain-
ing a slightly larger average particle size than the RP.
Analysis of size distribution by number suggests, however, that
the size distributions for RP and TWP are different. RP has a unimodal
size distribution by particle number, where TWP has a bimodal size
distribution by particle number. This bimodal distribution of particle
number is common for tires, and has been reported elsewhere (Fukahori
and Yamazaki, 1994b; Fukahori and Yamazaki, 1994a; Fukahori and
Yamazaki, 1995). It is thought that this wear phenomenon results from
two types of forces, microvibrations and stick-slip motion, applied to
the tire during use. These forces result in the generation of particles of
approximately 0–10 μm and several hundred μm, respectively (Fuka-
hori and Yamazaki, 1994a). While a bimodal size distribution by number
is common for tires, the bimodal distribution is not apparent for the RP,
which contains material from tires and other sources (e.g., exhaust
emissions, brake dust, pavement, environmental dust, etc.). This is likely
a result of normalization of the peaks in the size distribution by these
additional components of the particulate mixture. Only a very small
fraction of the RP (approximately 15%) originated from the tires on the
collection car (Supplementary materials).
Comparison of the chemical compositions of the RP, TWP, and TP can
provide insight into what effects the road surface and other traffic-
related sources can have on particulate generated from tire use. This is
essential in understanding which generation methodologies is appro-
priate for evaluating the toxicity of particles associated with tire use. The
results of the analyses performed in this study indicate that RP contains
metals and other elements associated with roadways and other traffic-
related sources in greater quantities than TP. TWP also contains metals
that are present in pavements in greater quantities than TP (and similar
to RP for those metals found in pavements). This indicates that both RP
and TWP contain pavement and other non-tire-related particulate, and
likely at substantial quantities. From a physical and chemical standpoint,
both RP and TWP differ from TP and from one another such that toxicity
data derived from the use of one should not be used interchangeably or
extrapolated to represent the toxicity of another.
One of the chemical families of particular interest in this study were
PAHs, because of the use of high aromatic oils containing PAHs in tire
manufacturing. In 2003, tires were alleged as a major contributor of
PAHs to the environment, and subsequently, the European Union
banned the use of high aromatic oils for use in tires, because they contain
PAHs (European Commission, 2005; KEMI, 2003). Contrary to this
decision, the data presented here suggest, as others have, that tires are
not likely a major contributor of PAHs to road dust (<150 μm), as
indicated by the low concentration of PAHs in TWP and TP when
compared to RP (Macias-Zamora et al., 2002; Rogge et al., 1993; Takada
et al., 1990; Zakaria et al., 2002). In fact, in some instances certain PAHs
are not detectable (<0.05 ppm) in either TWP or TP. However, there are
limitations in drawing such a conclusion. First, there are size limitations
(<150 μm) on the RP and TWP, and therefore we have not analyzed the
PAH content in TWP or RP in particles larger than 150 μm.
Second, it is unclear in a heterogeneous mixture such as TWP and RP,
what the relative efficiency of PAH extraction is for the different
contributors to the mixture. If rubber is not as efficiently extracted as
another component of RP, the relative contribution of tires to PAHs in RP
would appear artificially lower. However, the range of PAHs reported in
the TWP and TP in this study are within the lower part of the range
(approximately 10 ppm to 112 ppm) of predicted concentrations of PAHs
in tread from previous reported literature (based on range of PAH-
containing oils in tread formulation of approximately 4.5% to 16%)
utilizing a variety of extraction solvents (Czech-Scharif-Afschar, 1994;
European Commission, 2003; Nutt, 1984). Even in the presence of these
limitations, our results indicate that under harsh extraction conditions,
PAHs are not easily extracted from TWP or TP, indicating that the PAHs
present are less readily bio- or environmentally available than PAHs in RP.
Where previous studies have focused singularly on either street
dust, particles generated in a laboratory (under unrealistic conditions)
or tread rubber itself, few studies have characterized and quantified
differences in bulk particulate collected or generated from all three.
Furthermore, no existing studies evaluate the physical and chemical
characteristics of the unique entity, TWP, the particle generated upon
interaction with the pavement and the tire, in isolation.
5. Conclusion
From this study, we have demonstrated that both RP and TWP
contain a significant amount of material incorporated either from the
 M.L. Kreider et al. / Science of the Total Environment 408 (2010) 652–659
road or both the road and the surrounding environment, thus
decreasing the contribution, by mass, of rubber to the particulate.
Further work is necessary in order to more adequately define the
characteristics of the pavement that are important for particle
generation and/or toxicity of the particles. Continuing research
investigating the characteristics of the pavements used to generate
the particles used in this study (both RP and TWP), including chemical
composition is anticipated. Chemical analysis of the pavement is
currently underway. In addition, a series of toxicity studies with these
particles are planned. Combining results from toxicity studies with
physical and chemical characteristics of the particles or the pavement
will shed insight onto what risks, if any, tires or TWP may present
to human health or the environment.
Acknowledgements
The work presented here was funded by the Tire Industry Project,
an international consortium of 11 tire manufacturers, collaborating to
understand the human health and environmental impact of tires,
under the oversight of the World Business Council for Sustainable
Development. We would also like to acknowledge Christelle Darnaud
and others at Michelin Engineering Services, Klaus-Peter Glaeser,
Marek Zöller, and Gerd Stommel at Bundesanstalt für Straßenwesen
(BASt), Ana Barbur (Akron Rubber Development Laboratory) and
Benjamin Ferchaud and Claude Janin (Laboratoire de Recherches et de
Contrôle du Caoutchouc et des Plastiques: LRCCP) for their technical
expertise and laboratory assistance.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.scitotenv.2009.10.016.
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