Science of the Total Environment 803 (2022) 149832

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Automated identification and quantification of tire wear particles (TWP)

in airborne dust: SEM/EDX single particle analysis coupled to a machine
learning classifier
Juanita Rausch a,⁎, David Jaramillo-Vogel a, Sébastien Perseguers b, Nicolas Schnidrig a,
Bernard Grobéty c, Phattadon Yajan d
a
Particle Vision GmbH, Passage du Cardinal 11, 1700 Fribourg, Switzerland
b
Gradiom Sàrl, Avenue de Tivoli 4, 1700 Fribourg, Switzerland
c
Department of Geoscience, University of Fribourg, Chemin du Musee 6, 1700 Fribourg, Switzerland
d
Adolphe Merkle Institute, University of Fribourg, Chemin des Verdiers 4, 1700 Fribourg, Switzerland

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

• The increasing share of TWP in airborne

dust emphasizes the necessity of quan-
titative and reproducible methods.
• Automated single particle SEM/EDX
analysis in combination with ML is a re-
liable method to quantify TWP.
• Size-resolved PM80-1 concentration of
TWP and micro-rubber for an urban
background and a kerbside site are pre-
sented.
• Airborne dust is differentiated in tire
wear, metals, minerals and biogenic/or-
ganic particles in an automated run.
• PM10-2.5 mass concentrations from the
Sigma-2-SEM/EDX approach are in good
agreement with reference methods.

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

Article history: The share of non-exhaust particles, including tire wear particles (TWP), within the airborne dust and particularly
Received 7 May 2021 within PM10 has increased in recent years due to a significant reduction of other particles including exhaust road
Received in revised form 18 August 2021 traffic emissions. However, the quantification of TWP is a demanding task due to the non-specificity of tracers,
Accepted 18 August 2021
and the fact that they are commonly contained in analytically challenging low concentrations (e.g. Zn, styrene,
Available online 24 August 2021
1,3-butadiene, vinylcyclohexene). This difficulty is amplified by the chemical and morpho-textural heterogeneity
Editor: Philip K. Hopke of TWP resulting from the interaction between the tires and the road surface. In contrast to bulk techniques, au-
tomated single particle SEM/EDX analysis can benefit from the ubiquitous heterogeneity of environmental TWP
as a diagnostic criterion for their identification and quantification. For this purpose, we follow a machine-learning
Keywords: (ML) approach that makes use of an extensive number (67) of morphological, textural (backscatter-signal based)
Tire wear and chemical descriptors to differentiate environmental particles into the following classes: TWP, metals, min-
Non-exhaust particles erals and biogenic/organic. We present a ML-based model developed to classify airborne samples (trained by
Coarse mode >100,000 environmental particles including 6841 TWP), and its application within a one-year monitoring cam-
Micro-rubber
paign at two Swiss sites. In this study, the mass concentrations of TWP in the airborne fractions PM80-10, PM10-
SEM/EDX single particle analysis
2.5 and PM2.5-1 were determined. Furthermore, the particle size distribution and shape characteristics of 5621

⁎ Corresponding author.
E-mail address: juanita.rausch@particle-vision.ch (J. Rausch).

https://doi.org/10.1016/j.scitotenv.2021.149832
0048-9697/© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
J. Rausch, D. Jaramillo-Vogel, S. Perseguers et al.
Machine learning TWP were evaluated. A cut through a TWP by means of FIB-SEM evidences that the mineral and metal particles
Automated classification typically found in TWP are not only present on the particle surface but also throughout the complete TWP vol-
ume. At the urban background site, the annual average mass fraction of TWP and micro-rubber in PM10 was
1.8% (0.28 μg/m3) and 0.9%, respectively. At the urban kerbside site, the corresponding values were 6 times higher
amounting to 10.5% (2.24 μg/m3) for TWP, and 5.0% for micro-rubber.
© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
1. Introduction
In recent years, interest in the occurrence and concentration of tire
wear particles also referred to as tire/road wear particles (TWP resp.
TRWP) in the environment has drastically increased. In the field of air
pollution control, this increasing interest came in parallel with the sig-
nificant reduction of exhaust road traffic and other emissions (e.g.
Defra, 2018; EIONET, 2018; Lewis et al., 2019; EEA Air Quality in
Europe, 2020; Schweizerischer Bundesrat, 2018), which is the result of
successful technological measures, for instance, targeting a reduction
of elemental carbon (soot) generated by diesel engine combustion. As
a result, the share of non-exhaust particle emissions (i.e. freshly emitted
tire, break and road surface wear, as well as the resuspension of those
particles) and the interest in them has increased in relative terms
among the Particulate Matter (PM) fraction PM10 (Daellenbach et al.,
2020; Singh et al., 2020; Amato, 2018; Defra, 2018). In addition, due
to an ongoing and further expected increase in vehicle numbers, respec-
tively, kilometers traveled (https://www.eea.europa.eu/data-and-
maps/indicators/size-of-the-vehicle-fleet/size-of-the-vehicle-fleet-10)
and weight per vehicle - the latter due to a higher number of larger cars
and vehicle electrification - non-exhaust vehicular emissions are also
expected to increase in the future (Timmers and Achten, 2018). Besides
being dispersed into the environment through atmospheric deposition,
TWP can potentially be transported through road runoffs into water-
courses (Järlskog et al., 2020; Panko et al., 2013; Unice et al., 2019a,
2019b), especially during precipitation events. This is of relevance con-
sidering that the rubber from tire abrasion (specifically styrene, which is
a precursor of polystyrene) is classified as micro-rubber/microplastic
(Sommer et al., 2018). Therefore, assessing the impact of TWP on our
environment is not only relevant in the context of air pollution but
also because tire abrasion is one of the most important sources of
microplastic in wastewaters, rivers, lakes, and oceans worldwide (Cole
et al., 2011; Kole et al., 2017; Klöckner et al., 2019; Kooi et al., 2016;
Boucher and Friot, 2017; Machado et al., 2018; Peeken et al., 2018)
and in general in the environment (Birch et al., 2020; Järlskog et al.,
2020, 2021).
The toxicological effect of tire wear has been evaluated in recent
studies, however with contradicting results. Kreider et al. (2020) stated
that estimated daily exposure to respirable TWP including both typical
and worst case exposure scenarios (0.079 to 0.147 μg/m3) represents
a low risk to human health because the species- and time-adjusted
no-observed-adverse-effect-concentration (NOAEC) for respirable
TWP was estimated by the authors to be 55 μg/m3. However,
Daellenbach et al., 2020 found that coarse-mode (i.e. PM10-2.5) metals
from vehicular non-exhaust emissions and a component (SCOA: sul-
phur containing organic aerosols) interpreted by the authors to be de-
rived from TWP are major constituents of the oxidative potential (OP)
concentration in PM. OP is of great relevance because it is interpreted
to cause an oxidant/antioxidant imbalance in the human respiratory
system inducing inflammatory reactions, which increase the probability
of health effects like pulmonary and cardiovascular diseases (Crobeddu
et al., 2017; Liu et al., 2014). A further potential health risk could be re-
lated to the variety of metals that are incorporated into the tire rubber
upon use (iron, copper, zinc, etc. stemming from brake wear deposited
on the road surface). Those metals have the potential to leach into the
surrounding environment (Wagner et al., 2018).
2
Science of the Total Environment 803 (2022) 149832
creativecommons.org/licenses/by-nc-nd/4.0/).
It has been suggested in several studies that TWP have the potential
to release toxic substances (e.g. Zn, 6 PPD-quinone, non-polar organic
compounds, etc.) through leaching in aquatic environments (Wik and
Dave, 2006; Bejgarn et al., 2015; Gualtieri et al., 2005; Tian et al.,
2021). The most recent study (Tian et al., 2021) found high concentra-
tions of a tire rubber-derived chemical compound called 6PPD-
quinone, a highly toxic transformation product of the ubiquitous tire
rubber antioxidant 6PPD, in roadway runoffs collected in Seattle and
Los Angeles (USA). The concentrations were toxic enough to induce
acute mortality in certain fish species (coho salmon). The authors also
stated that, a priori, there is no reason to believe that coho salmon is
particularly sensitive to 6PPD-quinone with respect to other species.
A study on sediment samples (Marwood et al., 2011) concluded that
under environmental conditions TWP represent a low risk to aquatic
ecosystems under acute exposure scenarios. In this sense it is not clear
what could be the impact to human and aquatic organism health due
to exposure through ingestion/digestion and/or inhalation of airborne
TWP. Considering the above mentioned results, the toxicological effects
on human health caused by TWP in general and their potential residues
need still to be examined.
Some of the latest toxicological evidence combined with the fact that
tires have been estimated to transfer up to 12% of their mass into the en-
vironment over their lifetime (Unice et al., 2012) clearly indicates the
need of quantifying the concentrations of TWP in the various environ-
mental compartments (water, air and soil) to better understand
human and animal exposure.
However, there is only a moderate number of studies attempting a
quantification of TWP in environmental samples (e.g. Klöckner et al.,
2019; Järlskog et al., 2020, 2021) and particularly in the air (Kole et al.,
2017; Panko et al., 2013; Panko et al., 2018 and references therein;
Panko et al., 2019). According to Grigoratos and Martini (2014),
0.1–10 wt% of tire wear is released into the environment as airborne
PM10. Considering all cited studies in the review of Baensch-
Baltruschat et al. (2020) the contribution of TWP to PM10 was reported
to be up to ca. 11 wt%, whereas the highest absolute TWP concentration
in ambient air was reported to be 3.4 μg/m3 in a measuring campaign in
Granada, Spain (Amato et al., 2014).
A review of the current knowledge on tire wear emissions including
all available quantitative studies of TWP in the different PM fractions is
presented in Panko et al., 2018. Studies in Europe summarized therein
reported tread contributions to PM10 ranging between 0.1% (Sjödin
et al., 2010) and 10% (Israël et al., 1994).
The contrasting results of quantitative studies on TWP are mainly
due to differences in the site characteristics (density of road traffic and
driving behaviour), but also due to analytical challenges. One of the
main difficulties in quantifying tire wear lies in the complex nature of
these particles. Although, tires largely consist of tire rubber, in the envi-
ronment TWP occur as heterogenous mixtures of tire tread and road
wear, which is incorporated into the tire tread upon use. The variety
of existing tire (rubber) and road surface compositions (Gustafsson
et al., 2008) further complicates the quantification of TWP in environ-
mental samples. The degree of mixing of TWP depends on many factors
(e.g. driving speed, traffic flow, road characteristics, tire quality, meteo-
rological conditions, etc., Panko et al., 2018) resulting in complex envi-
ronmental TWP. It has also been suggested that tires undergo
chemical modifications through friction heat while in contact with the
J. Rausch, D. Jaramillo-Vogel, S. Perseguers et al.
road and natural dust, resulting in modification of the composition with
respect to the original one (Panko et al., 2013; Tian et al., 2021). All these
factors imply that TWP match only partially the original composition
and textural characteristics of the unused tire rubber (Kreider et al.,
2010), and thus the TWP found in environmental samples always ex-
hibit a modified and mixed fingerprint. In addition, commonly used
tracers are ambiguous (e.g. Zn and organic Zn) since they are also
often contained in other particle types very common in urban settings
like brake wear (Pant and Harrison, 2013) and anti-corrosion agents
typical of ubiquitous zinced surfaces (e.g. guardrails). Furthermore,
the mass concentration of Zn in TWP has been found to be significantly
lower than in tread particles because of mixing with the pavement
(Panko et al., 2018). Additionally, it has been experimentally demon-
strated that Zn can leach into the surrounding environment (Gualtieri
et al., 2005) making the use of Zn as a TWP tracer challenging. Other
used chemical markers for tread rubber are monomers styrene and
1,3-butadiene, which allow the qualitative confirmation of the presence
of TWP in environmental samples. The dimers vinylcyclohexene and
dipentene have been additionally used to quantify the TWP concentra-
tions owing their specificity for natural rubber (NR), styrene-butadiene
rubber (SBR), and butadiene rubber (BR) polymers, of which TRWP are
interpreted to be the primary source in the environment (Panko et al.,
2013; Panko et al., 2018; Panko et al., 2019). However, the low concen-
trations of these compounds make the quantitative analysis of TWP (e.g.
by pyrolysis GC/MS) challenging (Rauert et al., 2021; Unice et al., 2012).
Moreover, the identification of TWP by means of pyrolysis GC–MS fol-
lowing ISO technical specifications is based on considerable assump-
tions. This approach presumes a homogeneous natural and synthetic
rubber content in tire tread across formulations, as well as selective py-
rolysis products. Thus, this approach has been shown to have the poten-
tial to underestimate the TWP concentrations by a factor of 5 or even
more (Rauert et al., 2021). This could potentially further be influenced
by the sample preparation, which usually involves a density separation
step prior to analysis (e.g. Klöckner et al., 2019) potentially leading to
TWP loss. These difficulties have made the identification, differentiation
and quantification of TWP in environmental samples extremely time
demanding and challenging.
Single particle analysis by SEM/EDX (Scanning Electron Microscopy
coupled to Energy Dispersive X-ray spectroscopy) has been increasingly
used to characterize and recognize TWP in airborne samples (Sommer
et al., 2018; Kovochich et al., 2021). Both studies recognized tire wear
by SEM/EDX single particle analysis and concluded that this approach
has a great potential but is still largely limited by the lack of automatiza-
tion and standardization. Up to present, the main problems for an auto-
matic differentiation of TWP from other particle classes using chemical
fingerprints are (a) the complex and heterogeneous compositions of
TWP and (b) the composition of conventional substrate material,
which contains elements also present in TWP (C or Si). In this study,
we present the results obtained by an automated approach addressing
both problems to characterize, identify, and quantify TWP in the
PM80-10, PM10-2.5 and PM2.5-1 fractions of airborne samples. The
substrate problem was overcome by collecting particles on boron sub-
strates. The discrimination of TWP using automated SEM/EDX single
particle analysis was improved by combining the chemical fingerprints
(including the element carbon) with morphological and textural pa-
rameters as discriminators into a machine learning (ML) based particle
classifier developed in-house.
2. Methods
2.1. Design of case study
In the framework of a PM10 characterization and source apportion-
ment campaign on behalf of the Swiss Federal Office for the Environ-
ment (FOEN), samples were collected in two cities in Switzerland
(Bern, 540 m elevation and 133,115 inhabitants; and Zürich, 408 m
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Science of the Total Environment 803 (2022) 149832
elevation and 402,762 inhabitants). The station in Bern (named Bern
Bollwerk) represents an urban kerbside and the station in Zürich
(named Zürich Kaserne) is an urban background station (Fig. 1) of the
National Air Pollution Monitoring Network (NABEL) of Switzerland.
The measuring devices at Bern Bollwerk are located in the city center
besides the railway station and in the immediate vicinity (few meters
distance) of a main road (Bollwerk) with a daily traffic volume (DTV)
of ca. 15,000. In Zürich Kaserne, the situation is very different since
the measuring station is located in a courtyard shielded from the
roads by one to two storeys' high buildings. In the courtyard itself the
DTV is <20 and in the nearest main street (Kanonengasse, 50 m
away) the DTV is 4000. The sampling campaign took place over a period
of one year between June 2018 and June 2019 (Table 2, Supplementary
data). At each site, 24 samples with a sampling duration of 16 days each
were collected. A total of 42,241 particles were morpho-chemically an-
alyzed as described below (880 particles in average per sample exclud-
ing salt and miscellaneous particles, for further details on this type of
particles see Section 2.4). Additionally, in Bern Bollwerk, supplementary
11 samples were collected, whereas each sample was taken following a
sampling concept of every fourth day covering a duration of 32 days (i.e.
effective sampling of 8 days per sample). These samples allowed the
validation of the Sigma-2 SEM/EDX results for particulate mass and ele-
mental composition by comparison to the reference method (HIVOL fil-
ters sampled for an identical time period and subsequent analysis by
gravimetry and ICP-MS/OES). The results obtained with the Sigma-2
SEM/EDX method match the values obtained from the reference
method very well (Supplementary data and further details in the report
Rausch et al., 2020 on behalf of the Swiss FOEN).
2.2. Sampling equipment and material
Samples of the PM80-1 fraction were collected with the Sigma-2
passive sampler (VDI 2119:2013) on self-made, highly polished boron
surfaces (crystals made of 99.7% of boron were purchased from
Sigma-Aldrich, Merck Group). The advantage of boron substrates is
that - unlike commercially available conventional carbon-bearing sub-
strates for SEM/EDX analysis (i.e. C-pads, polycarbonate filters) - the el-
ement carbon (C) and other low-Z elements can be analyzed
quantitatively by EDX spectroscopy (Choël et al., 2005). The expected
error for the quantification of the element C will be, however, larger
compared to heavier elements, i.e. in the range of 1–10 wt% depending
on the analytical setup and particle characteristics (i.e. element distribu-
tion within the particle). The inclusion of C in the analysis is essential
because it is diagnostic for the identification of TWP, since among
their constituents are compounds such as carbon black, different poly-
mers as well as plasticizers and oil, all ingredients containing carbon
(Kreider et al., 2010). Furthermore, the use of boron substrates strongly
enhances the material contrast between the collected particles and the
substrate resulting in an optimized particle recognition in automated
single particle analysis and in better images, allowing a more detailed
morpho-textural characterization of the particles. Because of the un-
availability of carbon-free, low atomic number filters for active sam-
pling of PM10 and PM2.5, collection with a Sigma-2 passive sampler
on homemade boron substrates was chosen for the proposed character-
ization and quantification of airborne TWP. The latter device has been
validated by the Association of German Engineers (VDI 2119:2013
norm) and tested in various studies concluding that it is a reliable collec-
tor for airborne PM10–2.5 and PM80–2.5 (e.g. Dietze et al., 2006; Waza
et al., 2019). Even though the fraction PM2.5–1 collected with the
Sigma-2 passive sampler might result in underestimated values due to
lower sedimentation rates related to turbulent diffusive deposition
(VDI 2119:2013), it was also included in the analysis in order to present
at least minimum, and therefore conservative values for particles within
this fraction. Due to the relatively slow sedimentation rate of particles in
the size range of the coarse mode (PM10-2.5) and PM2.5-1, the sam-
pling interval chosen was 16 days (i.e. one period/sample = 16 days).
J. Rausch, D. Jaramillo-Vogel, S. Perseguers et al. Science of the Total Environment 803 (2022) 149832

Fig. 1. a–e) Maps showing the geographical location of the studied NABEL sites. b, d) Bern Bollwerk (urban kerbside site) and c, e) Zürich Kaserne (urban background site).

4
J. Rausch, D. Jaramillo-Vogel, S. Perseguers et al.
The Sigma-2 sampler inlet was at ca. 3.0 m height in Bern Bollwerk and
at 2.0 m height in Zürich Kaserne. For further details on the design of the
case study see Section 2.5.
2.3. Scanning Electron Microscopy and EDX analyses
2.3.1. Automated SEM/EDX single particle analysis
An area between 1 and 6 mm2 of each sample (area depending on
the particle load on the sample surface) was analyzed by automated
SEM/EDX single particle analysis (also known as CCSEM, computer-
controlled SEM). For this purpose, a Zeiss Gemini 300 Field Emission
Gun (FEG)-SEM equipped with an Oxford X-MAX EDX detector with
an 80 mm2 window, a high efficiency 4 quadrant BSE detector and the
particle analysis software AZtecFeature (©Oxford Instruments) at Parti-
cle Vision (Fribourg, Switzerland) was used. The analyses were per-
formed at 12 kV, with a 60 μm aperture and approx. 3.4 nA beam
current (measured with a Farraday cup). Image pixel size for the analy-
sis was 0.0559 μm (500 × magnification and resolution of 4096 × 3072
pixels per image). Particles deposited on the boron substrate were rec-
ognized by simple gray value (i.e. BSE intensity) thresholding. EDX
analyses were performed for each recognized particle with the
AZtecFeature software (©Oxford Instruments). A “ZAF” correction
(PAP version of the ϕ(ρz) formalism, (Pouchou and Pichoir, 1987)
was applied automatically by the Aztec software on the raw data to
calculate the elemental concentrations. The standard measurements
were performed using the factory delivered set. The ZAF procedure is
only correct for homogeneous samples with smooth surfaces per-
pendicular to the beam and considerably thicker than the diameter
of the excitation volume. Both are not the case for particles. But sev-
eral authors (Weinbruch et al., 1997; Meier et al., 2018; Kandler
et al., 2018) have shown that for particles larger than 1 μm in diam-
eter the relative 1σ standard deviation for corrected concentrations
of major element is in the range of 2%, whereas for minor elements it
is considerably larger (Kandler et al., 2018). As only particles with di-
ameters >1 μm (i.e. >250 pixels per particle) were considered in the
further processing of the data, the ZAF corrected values for the con-
centration were retained, without applying more sophisticated
correction procedures. The standard deviation in ZAF corrected con-
centration measured in particles is increasing proportional to the ac-
celeration voltage (equivalent to increasing excitation volume). The
value used for the measurements (12 kV) is the lowest possible in
order to excite useful characteristic X-ray lines for all elements pres-
ent in the sample. Several blank analyses of empty boron substrates
have shown, that under the applied analytical conditions the sub-
strate surface contains only the element boron and that in an area
of ca. 1 mm2 a maximum of five particles were present on unexposed
substrates. The latter are organic in nature and most likely follicles.
Together with the composition also nine basic morphological param-
eters for each analyzed particle were automatically determined by
the AZtecFeature software.
2.3.2. Characterization of the interior of a TWP by FIB-SEM
To gain complementary insights into the texture and elemental
composition of the internal structure a TWP was cut into two parts by
means of a Focused Ion Beam Scanning Electron Microscope (FIB-
SEM). TWP were partially embedded in epoxy resin to immobilize and
preserve the integrity of the sample. To make the sample conductive,
a thin layer of gold (~2 nm) was sputtered onto the sample surface be-
fore imaging. A Dual Beam microscope Thermo Scientific Scios 2
(Thermo Fisher Scientific) was used at the Adolphe Merkle Institute
(Fribourg, Switzerland) for the milling and imaging of individual TWP.
When a particle of interest was localized, a 1 μm thick platinum layer
coating was generated to protect the region of interest. To gain access
to the internal part of the TWP, an ion (Ga+) beam with 30 kV acceler-
ation voltage and a current of 1 nA was used to create a trench, followed
by a finer polishing step (30 kV, 0.3 nA) prior to imaging. The polished
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Science of the Total Environment 803 (2022) 149832
cross section was imaged by the SEM with an acceleration voltage of
5 kV and a current of 50 pA, while using an in-lens backscattered elec-
tron detector (BSE) with a dwell time of 30 μm at an image resolution
of 1536 × 1094 pixels.
2.4. Data treatment and particle classification by machine learning (ML)
Due to the properties of boron (e.g. hard and brittle) it is very
likely that the polished boron surface contains imperfections like
crevasses and pores, which can be erroneously recognized as parti-
cles by the AZtecFeature single particle analysis software. Therefore,
before data treatment (i.e. particle classification) a short manual
cleaning of these artefacts was performed. The cleaned data sets
were exported and subsequently treated with a ML-based algorithm
(see below and Supplementary data). In prior studies using single
particle analysis (e.g. Meier et al., 2018; Gottardini et al., 2021)
and ML-based classifiers (Luo et al., 2020; Christopoulos et al.,
2018; Crawford et al., 2020), either a purely chemical-based or a
morphological classification approach was used. The advantage of
the new ML-based classification algorithm presented in this study,
is that it makes use of both morpho-textural information and the el-
emental composition of each analyzed particle. Furthermore, in
comparison to the classifier for SEM/EDX particle data described in
Meier et al. (2018), it includes the elements carbon and oxygen
which is possible due to the use of boron substrates and a state-of-
the-art EDX detector that allows the analysis of light elements (C,
O, N). Besides the morphological parameters delivered by the
AZtecFeature software (size, circularity, aspect ratio, etc.), the
developed algorithm automatically extracts and calculates 23 com-
plementary morpho-textural parameters (e.g. fractal dimensions,
convexity, gray kurtosis, modified Ripley's K-functions, etc.). Some
of these parameters (fractals, solidity, and convexity), for instance,
were chosen because they turned out to have a high sensitivity to
small morphological variations as was observed for volcanic ash par-
ticle classes similar in composition but different in their formation
mechanisms (Pardo et al., 2020; Rausch et al., 2015). Parameters as
gray kurtosis, gray mean, gray standard deviation, etc. serve as de-
scriptors of the degree of heterogeneity of the particles. Such BSE-
signal based parameters will be referred as “textural” parameters
in this study. For instance, the BSE-signal of a mineral particle is
quite homogeneous across the entire particle whereas across a
TWP it is very heterogeneous.
For the particle classification all the available chemical and morpho-
textural descriptors are considered in a “random forest” model trained
with more than 100,000 particles from 41 different sites characterized
by contrasting source environments (i.e. urban, urban background,
rural, traffic, industrial, quarry); for details on the ML-model see Supple-
mentary data. In a first step, the classification model was trained with a
smaller data set (ca. 10,000 particles) by manual verification and com-
paring them with reference samples/particles (e.g. minerals, brake
wear, tire wear, organic particles like pollen and spores). Subsequently,
further training iterations with a larger data set were performed auto-
matically by the ML-algorithm and manually double-checked. This pro-
cess was repeated several times (with 20,000, 40,000, 80,000 particles)
until reaching a final robust classification for the following six morpho-
chemical classes: a) tire wear particles (TWP), b) metallic particles,
c) minerals, d) biogenic/organic particles, e) salt/salt mixtures, and
f) miscellaneous, consisting mainly of artefacts due to substrate irregu-
larities and particles/crystals formed by precipitation from liquid aero-
sol droplets (Table 1). For environmental samples the classes a-e
correspond to the most common particle classes found in coarse mode
dust. The validity of a division of particles in these specific classes is
also corroborated by the unsupervised two-dimensional reduction (t-
SNE algorithm) of the chemical and morpho-textural properties of all
particles used for training the classification model (including 6841
TWP) (Fig. 2a). Class e and f need, however, to be treated differently
J. Rausch, D. Jaramillo-Vogel, S. Perseguers et al. Science of the Total Environment 803 (2022) 149832

Table 1
Definition of the morpho-chemical classes differentiated by the ML-algorithm.

Particle class Definition Likely sources

Biogenic/organic Particles that mainly contain C and O with small amounts of ±N, S, K, P, Ca, Na, etc. e.g. biogenic (spores, pollen), organic matter (plant
particles fragments, bitumen-rich particles, etc.)

Minerals Particles showing a mineral fingerprint (often silicates, calcite or mixtures). They can be single crystals e.g. road wear, construction work, quarries,
or aggregates geogenic

Tire wear Mixed particles made of rubber and minerals originating mainly from the combination of tire and road e.g. road traffic
particles wear. They can also contain metallic particles (e.g. from brake wear deposited on the road surface)
(TWP) and/or bitumen wear. Elemental composition consists mainly of C, O, Si, S ± Ca, Al, Na, Mg, K, Fe, Zn,
Cu, Cr, Sb, Sn, Ti, etc.

Metallic particles Particles that mainly contain metals (very often Fe ± Si, Cu, Cr, Sb, Sn, Ba, Zn, O, etc.) e.g. road/railway traffic (brake wear, railway wear),
industry

Salt particles Crystals or mixed particles dominated by NaCl (halite). They occur predominantly in clusters e.g. road traffic (road salt), natural sea salt in case of
indicating that they were deposited as aerosol droplets. nearby oceans

Miscellaneous Cavities on the boron substrate erroneously identified/classified as particles; and precipitates other e.g. substrate and sampling “artefacts”
than halite originally deposited as droplets >PM10

than the other ones. Class e mainly consists of salt (halite) and salt mix-
tures precipitated from aerosol droplets > PM10 as can be concluded
from the deposition in clusters of these particles on the boron substrate
(Fig. 2f). These particles are analyzed and classified but not included in
the coarse mode fraction calculations since they would be eliminated
by impaction in a PM10 active sampling systems (for comparison of
Sigma-2-SEM-EDX coarse mode data with results from the reference
method see Supplementary data). Neither were particles classified as
f) miscellaneous included in the mass calculations (see Section 2.5)
since they correspond either to artefacts resulting from surface defects
on the substrate misinterpreted as particles by the particle recognition
routine (Fig. 2g) or precipitates other than halite (e.g. carbonate and sul-
fate clusters).
Once the training was finished, the classification algorithm was
run with new samples not included in the training set without
further supervision. In this study, we opted to abstain from small
corrections of potentially misclassified particles in favor of the
repeatability of the quantification. However, if desired, the classifica-
tion can be manually checked, and eventual corrections can be per-
formed by moving particles from one class to another (e.g. from
TWP to mineral particles). In this case, all results and calculations
made by routines included in the software are automatically updated
in the output tables and graphs, making this approach extremely
flexible and efficient.
The advantage of a ML-based particle classification is that every sin-
gle particle is judged based on all the available predictors (elemental
composition and morpho-textural parameters), and the algorithm de-
cides which class best fits the data, always following the same criteria.
This means that small variations in quantification of the elements do
not impact the quality of the classification.
The prediction accuracy that is expected from the developed ML-
classifier is shown in the Supplementary data (Fig. 9). To validate the
performance of the classifier in identifying and quantifying TWP, a pos-
itive and negative control was performed. For more details see Supple-
mentary data (Figs. 11 and 12).
2.5. Calculation of concentrations
Finally, after particle classification the number (CnP in particle/m3)
and mass concentration (Cm in μg/m3) for each particle class and for
the entire sample is calculated following the formulas summarized in
the norm VDI 2119:2013.
The automated SEM/EDX single particle analyses of the Sigma-2
samples deliver the size of the particles within the size range 1–80 μm
as 2D equivalent circular diameter (ECD). To calculate particle volumes
and masses, the 3D diameter was assumed to be equivalent to the 2D
ECD. The conversion from ECD to aerodynamic diameter is done accord-
ing to VDI 2119:2013 under consideration of the assigned densities for
each class (see below).
To extract the PM10-2.5 (coarse mode), respectively the PM2.5-1
fine fraction, the previously converted results (i.e. considering the
aerodynamic diameter of each particle) are treated by modeling
the corresponding separation efficiency curve according to both
CEN EN 481 (1993) (PM10 thoracic) and CEN EN 12341 (2014)
(PM10). Both result packages, which are obtained from calculations
following either norm, are created in automated manner by the clas-
sifier. For the calculation of the aerodynamic diameter and the mass
concentration within the respective sample a specific density is
assigned to each particle class (1.8 g/cm3 for TWP (corresponding
to the average density of the TWP density spectrum shown in
Klöckner et al., 2019), 5.1 g/cm3 for metallic particles (corresponding
to the approximate density of hematite), 2.7 g/cm3 for minerals (av-
erage density of most common minerals like silicates and carbon-
ates) and 1.0 g/cm3 for biogenic/organic particles. By using other
end-member densities for TWP reported for instance in Klöckner
et al. (2019, 2021), the TWP mass concentration within the coarse
mode (PM10–2.5) results to be 11% lower for a TWP density of
2.1 g/cm3 and 14% higher for a TWP density of 1.5 g/cm3, in annual
average. This exercise with different densities shows in which
order of magnitude the selection of the density or density variations
within the TWP class have an influence on the results.
The detection limit of any group (incl. TWP) depends on the
relative proportion (numberwise) of the group within a sample.
The number of particles required for having a lower 95% confidence
limit of the Poisson distribution >1 particle has been calculated
based on BGI/GUV-I 505-46 (2013) and VDI 2119 (2011, p.25). For
800 particles the detection threshold amounts for 0.5% in terms of
particle number, taking into account that in the blank samples no
TWP have been detected. The detection threshold is lower if a larger
number of particles is measured.

Fig. 2. a) Unsupervised two-dimensional reduction (t-SNE algorithm) of the chemical, textural and morphological properties of all particles (including 6841 TWP) used for training the
classification model. The main particle classes found in airborne samples are “naturally” clustered in this embedding. The main classes contain also subclasses, which correspond to
specific morphologies and/or chemical compositions (e.g. subgroups of the mineral class: mineral aggregates, mineral crystals, mineral spheres, etc.); b–g) Backscatter images of
typical particles for the corresponding classes.

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J. Rausch, D. Jaramillo-Vogel, S. Perseguers et al. Science of the Total Environment 803 (2022) 149832

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J. Rausch, D. Jaramillo-Vogel, S. Perseguers et al. Science of the Total Environment 803 (2022) 149832

Fig. 3. a) BSE image of the interior of a unused tire, i.e. showing the texture without secondary mineral and metal incrustations. The dark gray mass represents the rubber while the small
bright dots are Zn-additives (blue arrows); b) surface of a used tire with incrusted minerals (e.g. calcite, orange arrows) and metals (red arrows). The light gray mass corresponds to the
rubber matrix, while the dark areas are cavities. The marked outline (yellow line) shows a partially detached fragment which can potentially become a PM10 tire abrasion particle that
could break away from the surface and thereby be released into the environment. c–d) Corresponding sum spectra integrated over the entire surfaces shown in both images. (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

3. Results and discussion of case study
3.1. Characterization of TWP by SEM/EDX single particle analysis
Our results confirm previously published data (Kovochich et al.,
2021; Rausch et al., 2019; Sommer et al., 2018; Panko et al., 2013;
Kreider et al., 2010; Veith, 1995) in that TWP in environmental samples
do not match the original tire compositions (i.e. tire rubber including
additives). Once the tires interact with the road there is always a mixing
process between the tire and the material of and on the road surface.
This explains why TWP always have mineral and metallic incrustations
and, therefore, a higher content of elements contained in minerals (Si,
Ca, Al, Na, Mg, K, Fe, etc.) and in metallic particles (Fe, Cu, Cr, Sb, Sn,
etc.) than within unused tire rubber regardless of the brand and type.
The latter contains originally only the elements C (mainly present in
styrene-butadiene rubber, carbon black filler and in some formulations
calcite/chalk (CaCO3) filler), small amounts of SiO2 (present as silica
filler), and traces of S and ZnO (added as vulcanization agent and cata-
lyst, respectively) (Fig. 3). A question that has arisen from these findings
is whether the mixing of the mineral particles is only superficial or also
occurs inside the TWP found in environmental samples. A cut through a
PM10 TWP by means of a Focused Ion Beam Scanning Electron Micro-
scope (FIB-SEM) confirms that the mineral and metal particles are not
only present on the particle surface but also throughout the complete
TWP volume (Fig. 4). This is an important observation that contributes
to a better understanding of the nature of TWP found in the environ-
ment. In addition, it is important when it comes to estimate the amount
of traffic derived micro-rubber (microplastic) that is being introduced in
the environment (see Section 3.5).
The elemental composition and morphology of the different TWP
found in the environment is highly variable owing to different fac-
tors: (a) the aging/degree of reworking of the particles, (b) the com-
position of the road surface (e.g. asphalt type and filling material),
(c) the road configuration (curve, straight, roundabout), (d) the
driving behaviour (stop and go, constant velocity, braking), and
(e) the natural (e.g. nearby rock and soil outcrops) and anthropo-
genic (e.g. nearby construction works, quarrying and mining) dust
sources influencing the specific study site. It turned out that com-
bined chemical (C, O, Si, S ± Ca, Al, K, Mg, Na, Fe, Zn in variable pro-
portions) and morphological (e.g. solidity, convexity, fractal
dimension) as well as textural parameters, especially those describ-
ing the heterogeneity of the particles (e.g. gray mean, gray standard
deviation, etc.) were essential to successfully discriminate TWP from
the other particles in the collected samples.
By applying the above-described ML-algorithm, which combines
in total 67 morpho-textural-chemical predictors (i.e. values of
parameters) in a matrix, a rapid, accurate, and fully automated
classification of TWP and other environmentally relevant particles

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J. Rausch, D. Jaramillo-Vogel, S. Perseguers et al. Science of the Total Environment 803 (2022) 149832

Fig. 4. SEM images of a PM10 tire wear particle (TWP) sampled on a boron substrate. a) BSE image showing a TWP in the automated analysis mode; b) energy selective backscatter (EsBSE)
image at low kV visualizing the attached particles (sizes ranging from sub-micron to micron) making more visible the chemical heterogeneity and complex texture of the same particle as
shown in a; c) BSE image of the interior of a TWP. The incision of the TWP was performed with a Focused Ion Beam Scanning Electron Microscope (FIB-SEM). This image shows that the
particles are not only encrusting the surface of the TWP, but are also present inside.

(e.g. metal wear including brake abrasion particles, minerals and 3.2. Quantification of TWP in airborne samples from Switzerland
biogenic/organic particles, Table 1) can be achieved (see Supple-
mentary data). These other particle classes will not be discussed in The average number percentage of TWP per period (PM80–1) at the
detail in the present study but are also differentiated by default by urban kerbside site Bern Bollwerk amounts to 19.5% (192 particles per
the here applied ML-based classification approach in order to sample). The 95% confidence interval of that number of particles is 28
achieve a complete coarse mode mass estimation, particle differenti- particles based on the counting error (estimation of standard deviation
ation and source apportionment (Fig. 2). from Poisson distribution multiplied by 1.96, VDI 2119 2011 p.23),
which translates to a TWP share of 19.5 ± 2.8% according to the number
of particles. At the urban background site Zürich Kaserne, the average
Table 2 number percentage of TWP per period is 3.3% (41 particles). The
Annual mean values for the mass concentration (in μg/m3) of the total undifferentiated corresponding 95% confidence interval is extracted from the Poisson
particles in the respective size fractions (PM10, PM10-1, PM2.5-1, PM10-2.5 and PM80- distribution and amounts to 41 + 15/−11 particles, leading to a value
10) (uppermost part of the table). Mass concentration (in µg/m3) and the relative propor-
of 3.3 + 1.2/−0.9% in particle number.
tions (in %) of TWP (middle part of the table) and the rubber fraction of the latter (lower
part of the table) in the respective size fractions (PM80-10, PM10-2.5, PM2.5-1 and PM10) At Bern Bollwerk, an annual mean mass concentration of TWP
for both studied sites (Bern Bollwerk and Zürich Kaserne).The micro-rubber content cor- within the PM10-2.5 fraction of 2.17 μg/m3 was determined (mean of
responds to 47 % of the TWP concentration determined for the respective size fraction. 24 two-week periods). This accounts for 23% of the annual average of
Annual means (2018–2019) Bern Bollwerk Zürich Kaserne the coarse mode fraction (PM10-2.5) (values are valid for the measuring
period June 2018–June 2019). At Zürich Kaserne, the share of the TWP
μg/m3 μg/m3
in PM10-2.5 in annual average is 7% (0.27 μg/m3) (Table 2 and Fig. 5).
Total undifferentiated particles The temporal variability of the TWP mass concentration (μg/m3) at
PM10 (reference method)a 21.30 15.40
the studied sites shows a contrasting behaviour regarding the absolute
PM10-1 (Sigma-2-SEM/EDX) 10.90 4.70
PM2.5-1 (Sigma-2-SEM/EDX) 1.50 0.70 concentrations (Fig. 5). Whereas the results obtained from Zürich
PM10-2.5 (Sigma-2-SEM/EDX) 9.40 4.00 Kaserne show a low variability with a standard deviation (SD) of
PM80-10 (Sigma-2-SEM/EDX) 23.50 6.90 0.16 μg/m3, the SD in Bern Bollwerk was higher (SD = 1.13 μg/m3).
However, the relative SD for the temporal variability is similar at both
Annual means Bern Bollwerk Zürich Kaserne sites (59% and 52%, respectively). These fluctuations in PM mass con-
(2018–2019) centrations are typical of an urban canyon, as it is the case for Bern
μg/m3 % of the respective μg/m3 % of the respective
Bollwerk. For urban background sites, more steady concentrations of
fraction fraction
PM in general are expected (Hueglin et al., 2005; Putaud et al., 2004 &
Tire wear particles (TWP)
2010). The clear difference between the two locations reflects the con-
Total (PM80-1) 13.47 39.2 1.51 13.0
PM80-10 11.23 47.8 1.22 17.7 trasting influence of TWP in the immediate vicinity of a heavily traffic-
PM10-2.5 2.17 23.1 0.27 6.8 loaded road with typical stop and go driving behaviour compared to
PM2.5-1b 0.07 4.7 0.01 1.4 urban background sites.
PM10-1b 2.24 20.6 0.28 6.0 Even though the actual data does not include particles <1 μm and
b
PM10 2.24 10.5a 0.28 1.8a
the values obtained for PM2.5-1 need to be seen as minimum values
Micro-rubber content due to the limitations of the passive sampling method, one can never-
Total (PM80-1) 6.33 18.4 0.71 6.1 theless calculate a minimum estimate of the share of TWP within the
PM80-10 5.28 22.5 0.57 8.3
health relevant fraction PM10. This calculation is in fact a good estima-
PM10-2.5 1.02 10.9 0.13 3.2
PM2.5-1b 0.03 2.2 0.00 0.7 tion for the mass concentration of TWP within PM10 because of the size
PM10-1b 1.05 9.7 0.13 2.8 distribution inherent to them (see Fig. 6c) and the fact that the mass of
PM10b 1.05 5.0a 0.13 0.9a particles scales with the third power of their diameter. The measured
a
For the percentage calculations of TWP within PM10, the total PM10 concentrations TWP concentrations within the sum of the size fractions PM10-2.5 and
obtained from the gravimetrically corrected Fidas values determined by the EMPA on be- PM2.5-1 (or in other words within PM10-1) amounts in annual average
half of the FOEN were used (data source: NABEL).
b
2.24 μg/m3 at the kerbside site Bern Bollwerk and 0.28 μg/m3 at the
The tire wear and micro-rubber concentrations determined by Sigma-2-SEM/EDX
urban background site Zürich Kaserne. If we contextualize these results
only take into account particles down to 1 µm. It means that concentrations of TWP < 1 µm
are not reported in this study. In addition, the concentrations in the fraction PM2.5-1 with the official PM10 concentrations obtained from the gravimetric
might be underestimated due to limitations of the passive method. method (sampling device Digitel DHA-80) and the optical method

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J. Rausch, D. Jaramillo-Vogel, S. Perseguers et al.
(PALAS FIDAS 200) from the NABEL network (annual average
PM10: 21.3 μg/m 3 at Bern Bollwerk, and 15.4 μg/m 3 at Zürich
Kaserne, see Table 2), the measured TWP concentrations translate
to a share of 11% and 2% in PM10 in Bern Bollwerk and Zürich
Kaserne, respectively (Table 2). These values (especially for the
urban background site Zürich Kaserne) are in reasonable agree-
ment with other urban background sites presented for instance in
Panko et al. (2013). The authors determined PM10 concentrations
of TWP by pyrolysis GC/MS ranging between 0.05 and 0.7 μg/m3
(0.8% average contribution to PM10). Our results are in the same
order of magnitude when considering the higher values given in
the above mentioned study.
The present results emphasize the significance of TWP and in gen-
eral of “non-exhaust” abrasion particles (including also metal wear par-
ticles) as an important source of pollution in PM10-2.5 and PM10,
especially in heavily traffic-loaded areas.
3.3. Size-resolved mass and number concentration of TWP
The size-resolved mass concentrations of the four differentiated
morpho-chemical classes in the size range 1 to 80 μm ECD (equivalent
circular diameter) have been extracted for both Bern Bollwerk
(Fig. 6a) and Zürich Kaserne (Fig. 6b). Regarding the mass, TWP contrib-
ute appreciably over the complete spectrum of particle sizes with the
highest concentrations for the fraction >10 μm. At Bern Bollwerk,
11.23 μg/m3 of TWP were determined within the PM80-10 fraction (an-
nual average) accounting for 83% of the total identified TWP at this site,
while 17% of the TWP were contained in the PM10-1 fraction. It is also
remarkable that at Zürich Kaserne, the total TWP concentrations are
much lower by a factor of 9, but the relative contribution of the different
size fractions (79% TWP within PM80-10 and 20% within PM10-1) ex-
hibits only small variations in respect to Bern Bollwerk (Fig. 7a and
Table 2).
The relative mass contribution of TWP within the total mass of
PM80-1 tends to increase towards larger size fractions compared to
the other morpho-chemical classes (see Figs. 6a, b). This is in part due
to the fact that the contribution of the other sources (metallic, mineral
and biogenic/organic particles) markedly decreases. This is especially
true for the relative contribution in terms of mass concentration of the
non-exhaust “companion” metallic particles which is largely concen-
trated in the fine fractions (<10 μm ECD).
Even though it can be extracted from the particle size data that at
both studied sites the total mass concentration (i.e. the sum of all parti-
cle classes) reaches a maximum at particles <10 μm, there are at least
two differences between both sites that are worth to be discussed.
First, when considering mass concentrations, the particle size distribu-
tion in Bern Bollwerk is wider (Fig. 6a). This is clearly due to the greater
influence of coarser particles than in Zürich Kaserne, where a narrower
size distribution is present (particles mostly <30 μm) (Fig. 6b). Sec-
ondly, a subtle difference can be detected in the size distribution of
the TWP between the two sites (Fig. 6e). For instance, the mean particle
size of TWP at Zürich Kaserne is 18.55 μm with a 90% confidence interval
equal to [17.88, 19.22], while these values are 19.75 μm and [19.45,
20.05] at Bern Bollwerk; statistics are estimated via the bootstrap
method considering the parameter Cm (mass concentration in μg/m3)
as a sampling weight. The same procedure can be applied for calculating
the median of the particle size, leading to 90% confidence intervals of
[15.08, 16.74] and [16.83, 17.46] for Zürich Kaserne and Bern Bollwerk,
respectively. Compared to the markedly higher TWP concentrations in
Bern Bollwerk, the difference in size mean and median between both
sites is remarkably low. This indicates that the size distribution of
TWP in this particular case is nearly unaffected by the differences in dis-
tance to the source. This implies that the different mass concentrations
between both sites are mainly controlled by differences in the nearby
traffic volume (much higher in Bern Bollwerk: ca. 15,000 DTV than in
Zürich Kaserne: ca. 4000 DTV), and possibly also by the driving
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Science of the Total Environment 803 (2022) 149832
behaviour (stop and go in Bern Bollwerk) and urban canyon configura-
tion of the site.
The size-resolved number concentrations (CnP in particles/m3) of
the four differentiated morpho-chemical classes within the size range
1 to 80 μm ECD (Bern Bollwerk, Fig. 6c; Zürich Kaserne, Fig. 6d) show
clearly that the CnP of the sum of all particle classes increases exponen-
tially with decreasing particle sizes at both sites. This behaviour is rele-
vant for health effects since it implies that even in cases of low mass
concentrations, high number concentrations are possible. High CnP's
and therefore, high particulate surface areas, may affect the human re-
spiratory system (Bogunia-Kubik and Sugisaka, 2002). More detailed
representations of the number-based size distribution of TWP (inset
graphs in Fig. 6c and d), show that the amount of TWP is markedly
lower in Zürich Kaserne (4139 TWP/m3 in annual average) than in
Bern Bollwerk (35,759 TWP/m3 in annual average). These values in-
clude the entire size spectrum 1–80 μm. Interestingly, the relative pro-
portion of the smallest particles (<4 μm) is notably higher in Bern
Bollwerk suggesting that close to a source with large DTV, the contribu-
tion of small particles is higher than at larger distances to the source
(e.g. Zürich Kaserne).
3.4. Morphology of TWP
A further interesting result of the morphological examination of
TWP is that there does not seem to be an overall tendency of these par-
ticles to be elongated or “cigar/sausage-shaped” as described by other
authors (Adachi and Tainosho, 2004; Williams and Cadle, 1978;
Dannis, 1974; Kreider et al., 2010; Unice et al., 2012; Williams and
Cadle, 1978). TWP can be both, elongated and nearly round (79% of an-
alyzed TWP exhibit an aspect ratio < 2, 47% < 1.5, and 14% < 1.2 at both
studied sites) (Fig. 7). These results are in good agreement with the rel-
ative proportion of rounded vs. elongated TWP presented in Kovochich
et al., 2021. The mean aspect ratio of TWP in Zürich Kaserne is 1.53, and
in Bern Bollwerk 1.55. The average aspect ratio is 1.66 and 1.69, respec-
tively. There is no obvious correlation between the TWP size and the as-
pect ratio (Fig. 7b). This is of relevance when defining morphological
parameters for the identification of TWP when a complementary chem-
ical approach like EDX is not feasible (e.g. light microscopy analysis).
3.5. Estimation of the amount of rubber (microplastic) vs. mineral and me-
tallic incrustations
The concentrations presented in Sections 3.2 and 3.3 all refer to en-
vironmental TWP i.e. including mineral and metal incrustations. By sep-
arating the average mineral and metal content from the rubber matrix
of all environmental TWP measured at the two sites (4624 particles in
Bern Bollwerk and 997 in Zürich Kaserne), an average content of
micro-rubber (microplastic) could be estimated. An issue is elements
present both in the rubber matrix and in either metal or mineral incrus-
tations (e.g. C which is in both rubber and calcite). In this study, the cal-
cium content measured within the TWP could be mainly related to
incrustations of the mineral calcite (Figs. 2b, 4b) and not to the rubber
matrix (Fig. 2a). However, considering that in some tires Ca is present
in form of calcite or chalk as a filler in the rubber matrix (Waddell and
Evans, 1996), it cannot be completely excluded that a part of the Ca is
bounded in the rubber. Nevertheless, since this Ca occurs also as
CaCO3, in order to calculate the rubber content (excluding potential
calcite and chalk fillers) the following assumptions were done:
- The entire calcium measured in TWP was present as CaCO3 either as
mineral incrustation from road dust or as calcite/chalk filler.
- Tire rubber consists almost exclusively of carbonaceous compounds
(Fauser et al., 1999). Therefore, the elements H and O are not consid-
ered in the calculations for the rubber mass. This might lead to a
small C overestimation due to mass compensation of CHO com-
pounds.
J. Rausch, D. Jaramillo-Vogel, S. Perseguers et al. Science of the Total Environment 803 (2022) 149832

Fig. 5. a) Average of all 24 sampling periods (16 days duration each) of the mass concentrations (μg/m3) and relative proportions (%) of all morpho-chemical classes within the coarse
mode (PM10-2.5) for the NABEL measuring stations Bern Bollwerk and Zürich Kaserne. b–c) Temporal variation of the concentrations at both sites during the one-year measurement cam-
paign 2018–2019.

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J. Rausch, D. Jaramillo-Vogel, S. Perseguers et al.
- Therefore, the C content that corresponds to the rubber in TWP is
assumed to be equal to the content of plasticizers and oils +
polymers + carbon black reported in Kreider et al., 2010.
Based on these assumptions the following calculations were per-
formed:
- Based on the average Ca content within the TWP the corresponding
C content was calculated assuming that all Ca is present as CaCO3.
- The resulting C (i.e. bounded in CaCO3) content was subtracted from
the average total C content measured within the TWP.
- The relative proportion of the remaining C content in respect to the
concentration of the total TWP was calculated. Based on these
calculations 39.6% of the measured C was assigned to the rubber ma-
trix in the TWP. This value is in good agreement with the sum of av-
erage values for carbonaceous compounds (plasticizers and oils
(10 wt%) + polymers (16 wt%) + carbon black (13 wt%), sum =
39%) determined within TWP by thermogravimetric analysis by
Kreider et al. (2010).
- Owing the good agreement of the relative contribution of the carbo-
naceous compounds and the measured C content by SEM/EDX, the
average percentage of additives in tire rubber was adopted from
Kreider et al., 2010 (16% within a virgin tire tread). The additives
mass was consequently added to the rubber mass, resulting finally
in a proportion of 47% of tire rubber (including additives) vs. 53%
of mineral and metallic incrustations in average for all measured
TWP in Bern Bollwerk and Zürich Kaserne.
Based on these calculations the micro-rubber fraction amounts to
47% ± 5% on average of the environmental TWP measured at both
studied sites. This calculation is in good agreement with previous
studies that have also proposed a composition of ca. 50% rubber
and 50% incrustations for TWP (Kreider et al., 2010; Panko et al.,
2013; Unice, 2013).
This means that 6.3 μg/m3 micro-rubber/microplastic was found in
the PM80-1 fraction, 1.02 μg/m3 in the PM10-2.5 and 1.05 μg/m3 in
the PM10 fraction of the kerbside site Bern Bollwerk for the measuring
campaign 2018–2019. The micro-rubber/microplastic content at the
urban background site Zürich Kaserne accounts for 0.71 μg/m3,
0.13 μg/m3 and 0.13 μg/m3 in PM80-1, PM10-2.5 and PM10, respec-
tively. The relative contribution to the corresponding fractions is given
in Table 2. The remaining volume/mass of TWP corresponds to minerals
and metals.
4. Strengths, uncertainty/limitations, and potential future work
The automated SEM/EDX single particle analysis method coupled to
a ML-based classification (presented above) successfully recognizes,
and quantifies TWP along with mineral, metallic and biogenic/organic
particles in an automated manner and in one single analytical run. The
micrometric resolution of EDX analyses and the large number of param-
eters (67 particle descriptors) being recorded are able to capture the
large heterogeneity of TWP. This comprehensive data acquisition is
crucial for the successful recognition and quantification of TWP in
environmental samples. The method works for a large spectrum of tire
types and brands independent of the tread formulations. Number and
mass concentrations of the different particles classes - important for
regulatory purposes - can be determined by assuming a specific density
per class (see uncertainty related to this below). In addition, valuable
Fig. 6. Size-resolved mass (bars and left vertical axis) concentrations of the main morpho-chemical classes in Bern Bollwerk, a), and Zürich Kaserne, b) for the complete measurement
campaign 2018–2019. Size-resolved number concentrations of the main morpho-chemical classes in Bern Bollwerk, c), and Zürich Kaserne, d). The scale in a) and b), respectively
c) and d) are identical to make comparisons easier. e) Comparison of the grain size mass distribution of all TWP from the 2018–2019 one-year measuring campaign in Bern Bollwerk
(4624 particles) and in Zürich Kaserne (997 particles). Cm: mass concentration in μg/m3; CnP: number concentration in particles/m3; ECDMicron: Equivalent Circular Diameter in μm;
Blue and orange lines in e) are showing the median for Zürich Kaserne and Bern Bollwerk, respectively, with the corresponding 90% confidence intervals. (For interpretation of the refer-
ences to color in this figure legend, the reader is referred to the web version of this article.)
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Science of the Total Environment 803 (2022) 149832
morphological information is available like particle size distribution,
shape and textural parameters, which are crucial for the understanding
of particle formation, aging, transport, and deposition.
However, the passive sampling method has inherent limitations
due to the lower sedimentation rate of smaller particles, which limits
the application of this sampling method to particles >2.5 μm (if
quantitative studies are aimed). Therefore, the results obtained in
this study for the small fraction PM2.5-1 should be seen as minimum
estimates. Another limitation of passive sampling is the low tempo-
ral resolution since sampling intervals are ideally between 1 and
4 weeks to achieve an optimal particle distribution on the substrates.
However, in some cases this could be beneficial for monitoring pur-
poses, as a smaller number of samples can be used to cover larger
time intervals without gaps. The main uncertainties related to the
calculation of the concentrations include the fact that the used den-
sities for the different particle classes are not measured but esti-
mated based on the elemental compositions obtained from EDX
measurements, and on the typical densities of the main particles in
each class found in the literature. By using end-member densities
for TWP reported in Klöckner et al., 2019, 2021, the uncertainty of
the TWP mass concentration within PM10–2.5 calculated in this
study is −11% for a TWP density of 2.1 g/cm3 and +14% for a TWP
density of 1.5 g/cm3, in annual average. Another uncertainty is re-
lated to uneval number of particles in the individual size fractions.
In general, the larger the particles the less particles will be measured
per analytical run. Therefore, the size spectrum to be covered in one
analytical run has to be carefully chosen in order to guaranty that a
statistically representative number of particles will be measured
for each size bin. In the actual study this was optimized for the size
fraction PM2.5-10.
The volume and subsequent mass calculations for single particles are
subjected to another uncertainty due to the use of the 2D diameter to
calculate the 3D volume. A comparison of the Sigma-2 passive
sampler-SEM-EDX coarse mode (PM10-2.5) concentrations with results
obtained from the reference method (HIVOL-gravimetry) shows, how-
ever, a very good agreement (concordance correlation coefficient of
0.79 for Bern Bollwerk, and 0.87 for Zürich Kaserne, see Supplementary
data, Fig. 8) validating the quantitative determination of the total mass
concentrations, indicating that the values for the single particles and in-
dividual particle classes within the PM10-2.5 fraction can also be taken
with some confidence.
The smaller the particles, the lower the amount of pixels per particle,
and therefore, the amount of morpho-textural information available for
their classification. This makes the classification of smaller particles
more uncertain compared to larger particles. This can, however, be
overcome by adjusting and optimizing the analytical parameters for a
smaller particle size fraction (e.g. PM2.5) assuming that a quantitative
sampling is guaranteed.
The sampling and subsequent single particle analysis of TWP within
PM2.5 is challenging because a SEM suitable and C-free filter/surface is
necessary. Future work could envision an optimization of the quantifi-
cation of TWP within the PM2.5 fraction. In particularly, because it can-
not be excluded that TWP also play a role in PM2.5, especially if number
concentrations and the presumed toxicity of the tread components
(Gualtieri et al., 2005; Wik and Dave, 2006; 2009; Grigoratos and
Martini, 2014; Bejgarn et al., 2015; Tian et al., 2021) are considered.
The analytical approach to identify and quantify these particles within
the PM2.5 fraction is challenging since particles in this size range need
to be sampled actively. For instance, all commercially available filters
J. Rausch, D. Jaramillo-Vogel, S. Perseguers et al.
Fig. 7. a) Distribution of TWP within the different airborne fractions (PM80-10, PM10-2.5, PM2.5-1). Data from the 2018–2019 one-year measurement campaign in Bern Bollwerk and
Zürich Kaserne (NABEL sites, Switzerland). b) Aspect ratio vs. particle diameter (ECD = equivalent circular diameter) for all analyzed TWP (4624 particles from Bern Bollwerk and 997
particles from Zürich Kaserne). c) BSE images of individual TWP with their corresponding elemental composition in the different size fractions.
interfere with the chemical composition of the TWP (e.g. carbon content
of polycarbonate filters). Consequently, either a specially dedicated fil-
ter, or sampling surface needs to be developed or an adapted classifica-
tion scheme needs to be tested and validated to achieve a quantification
of TWP < 2.5 μm. Alternatively, mass-based techniques (e.g. pyrolysis
GC/MS) should be envisioned to quantify TWP in PM2.5.
The SEM/EDX single particle analysis and ML-based classification
approach proposed herein can be applied to road dust and water
samples (e.g. runoffs, rivers, lakes) as well, provided that the sam-
ples are properly prepared and the particle training set for the classi-
fication is updated with fingerprint samples from the specific
environments. The quantification of TWP and other pollutants like
metallic particles in aqueous environmental samples will be the tar-
get of future studies.
5. Conclusions
In this study, we present an automated ML-based technique to
differentiate and quantify TWP using morpho-textural-chemical
data acquired by means of automated SEM/EDX single particle anal-
ysis on environmental airborne samples collected passively on
boron substrates. In addition to TWP and in the same analytical
and data treatment run, mineral, metallic, and biogenic/organic
particles are differentiated and quantified, as well. Hence, the
method delivers high throughput and an objective and repeatable
classification.
As recent studies stated, there is a clear need to reliably quantify
TWP in the environment and to standardize the methodology (Rauert
et al., 2021; Kovochich et al., 2021) to achieve reproducible and compa-
rable results. We consider the approach presented in this study to be a
significant step towards this goal since it is an automated approach
and enables the possibility of examining not only the mass but also
the number concentration of TWP and other common particles in the
PM10-2.5 and PM80-10 airborne fractions in a certain sample within
14
Science of the Total Environment 803 (2022) 149832
the frame of the same analysis. This implies that the mass concentration
can also be related to specific size ranges delivering a comprehensive
overview of the variety of particulate matter and the source contribu-
tion at the sites of interest. This can be very useful when planning abate-
ment measures and assessing the potential health impact of a certain
particle class.
This method can represent a good complement to other TWP quan-
tification techniques (e.g. mass-based) when size, morphology, degree
of mixing and an overview of other particle types within the same sam-
ple is of interest.
The results presented in this study clearly show that even though the
mass concentration of TWP in airborne samples is dominated by the size
fraction >10 μm, a considerable percentage of TWP is still present in
smaller fractions, especially close to heavily traffic-loaded roads, such
as the studied kerbside in Bern, Switzerland (e.g. 10.5% of PM10;
2.2 μg/m3). This case study shows that TWP are an important source
of pollution in the air affecting both the coarse mode (PM10–2.5) and
the PM10 fraction in general.
CRediT authorship contribution statement
Juanita Rausch: Conceptualization, Methodology, Investigation, Vi-
sualization, Writing – original draft. David Jaramillo Vogel: Conceptual-
ization, Methodology, Investigation, Validation, Visualization, Writing –
review & editing. Sébastien Perseguers: Software, Writing – review &
editing. Nicolas Schnidrig: Validation, Formal analysis, Writing – re-
view & editing. Bernard Grobéty: Methodology, Writing – review &
editing. Phattadon Yajan: Investigation.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
J. Rausch, D. Jaramillo-Vogel, S. Perseguers et al.
Acknowledgements
We are grateful to the Swiss Federal Office for the Environment
(FOEN) for their financial contribution and support in the frame of the
PM10 characterization project at the two Swiss NABEL sites
2018–2019. The Swiss National Air Pollution Monitoring Network
(NABEL) is sincerely thanked for providing the PM10 and PM2.5 gravi-
metric and optical data. We thank Mario Meier (FUB AG) and Thomas
Zünd (mz partner Gmbh) for the collaboration in an early stage of the
methodology and their help changing the samples in Bern and Zürich.
René Locher (IDP, ZHAW) and Christoph Neururer (Department of
Geosciences, University of Fribourg) are kindly thanked for their pro-
gramming and technical support in a preliminary version of the autom-
atization of the SEM-EDX classification approach. Patrick Dietsche
(Department of Geosciences, University of Fribourg) is kindly thanked
for the technical advice for the production of the boron substrates. We
thank Jose David Avellaneda (EAFIT) for his help with the preparation
of the data set prior to classification (export, etc.). Brigitte Gälli Purghart
(FOEN) is thanked for the thorough revision of an early version of the
manuscript. We greatly thank the enriching corrections and suggestions
of the reviewers and editor.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2021.149832.
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