Atmospheric Environment 148 (2017) 102e114

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

Oxidative potential of on-road fine particulate matter (PM2.5)

measured on major freeways of Los Angeles, CA, and a 10-year
comparison with earlier roadside studies
Farimah Shirmohammadi a, Dongbin Wang a, Sina Hasheminassab a, Vishal Verma b,
James J. Schauer c, Martin M. Shafer c, Constantinos Sioutas a, *
a
University of Southern California, Department of Civil and Environmental Engineering, Los Angeles, CA, USA
b
University of Illinois at Urbana-Champaign, Department of Civil and Environmental Engineering, Urbana-Champaign, IL, USA
c
University of Wisconsin-Madison, Environmental Chemistry and Technology Program, Madison, WI, USA

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

On-road measurements of fine par-

ticulate matter (PM2.5) on roadways
of Los Angeles.

Oxidative potential of PM2.5 quanti-
fied using the dithiothreitol (DTT)
assay.

A 10-year comparison of PM2.5
chemical composition to previous
near-road measurements.

Increased levels of on-road DTT ac-
tivity in comparison to previous
dynamometer studies.

Results from this study highlights the
importance of non-tailpipe
emissions.

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

Article history: This study describes on-road measurements of fine particulate matter (PM2.5) using a mobile instru-
Received 29 July 2016 mentation platform to assess the chemical composition and oxidative potential of PM2.5, using the
Received in revised form dithiothreitol (DTT) assay, over three representative roadways in the Los Angeles Basin: the I-110 and I-
25 October 2016
710 freeways, the Wilshire/Sunset boulevards as well as the main campus of the University of Southern
Accepted 26 October 2016
California (USC), used as a reference urban background site. Samples were chemically analyzed for
Available online 27 October 2016
elemental carbon (EC), organic carbon (OC), polycyclic aromatic hydrocarbons (PAHs) and 50 elements.
The cumulative mass fraction of the measured PAHs was highest on the freeways (0.16 ± 0.01 and
Keywords:
Particulate matter
0.15 ± 0.01 ng/mg PM, on I-110 and I-710, respectively); which on average was 3 and 3.3-fold higher than
Oxidative potential at Wilshire/Sunset and USC site, respectively. Mass fractions of Ba, Cr, Cu, Mn, Ni, Pb, Sb and Zn, tracers of
Dithiothreitol (DTT) assay vehicular abrasion, were 3.8 ± 0.8 times higher on both freeways in comparison to Wilshire/Sunset. The
Tailpipe and non-tailpipe emissions observed intrinsic (normalized per PM mass) DTT activity was greatest on freeways, averaging
Metals and elements 30.13 ± 3.15 nmol/min mg PM and being roughly 1.9 and 2.1 times higher than the values obtained at
EC and OC Wilshire/Sunset and USC, respectively.
Furthermore, comparison of our results with previous on-road and roadside studies conducted in the
last decade in Los Angeles indicated an overall reduction in the contribution of carbonaceous species and
PAHs (important tracers of exhaust emissions) to PM mass, especially on I-710 freeway with the higher

* Corresponding author.
E-mail address: sioutas@usc.edu (C. Sioutas).

http://dx.doi.org/10.1016/j.atmosenv.2016.10.042
1352-2310/© 2016 Elsevier Ltd. All rights reserved.
 F. Shirmohammadi et al. / Atmospheric Environment 148 (2017) 102e114 103

heavy-duty diesel vehicle fraction, indicating the effectiveness of diesel vehicle emissions control policies
implemented in recent years in California. In contrast, greater contributions of certain groups of metals
and trace elements that are indicators of non-tailpipe emissions compared to previous studies provide
evidence on the increasing importance of non-tailpipe emissions to the oxidative potential of on-road
PM2.5 as vehicular exhaust emissions becomes cleaner. This finding was also reflected in the increased
levels of on-road DTT activity by factors of 1.4e1.5 in comparison to the DTT activity of vehicular
emissions estimated in previous dynamometer studies.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction conditions and atmospheric dilution are remarkably different from

Vehicular emissions are one of the most significant primary
sources of ambient particulate matter (PM) in metropolitan areas
(Kleeman et al., 2000; Schauer, 2003; Phuleria et al., 2007). In
California, approximately 25e30%, on an annual average basis, of
fine particulate matter (PM2.5, particles with aerodynamic diameter
less than 2.5 mm) have been attributed to primary emissions from
vehicles (CARB, 2013; Hasheminassab et al., 2014). Populations
exposed to these emissions in the proximity of heavily trafficked
roadways are more likely to be affected by adverse health outcomes
attributable to PM (Wilhelm and Ritz, 2003; Brugge et al., 2007;
Gauderman et al., 2007; McConnell et al., 2010). There is an
extensive body of literature linking exposure to PM with health
outcomes, ranging from cardiovascular and respiratory diseases to
neurological disorders (Delfino et al., 2010b; Li et al., 2008; Morgan
et al., 2011; Rich et al., 2013). The generation of reactive oxygen
species (ROS) has been postulated to be an important mechanism
leading to PM-induced toxicity and associated adverse health ef-
fects (Dellinger et al., 2001; Xia, 2007; Li et al., 2008). Oxidative
stress in cells results when the amount of generated ROS exceeds
the normal ranges which can be compensated by endogenous an-
tioxidants (Li et al., 2009). Several components of PM such as
transition metals, polycyclic aromatic hydrocarbons (PAHs) and
their oxygenated derivatives (e.g. quinones) have been linked to PM
oxidative potential (Wilson et al., 2002; Cho et al., 2005; Li et al.,
2008).
High-traffic roadways, where elevated concentrations of PM are
observed, play an important role in the overall exposure to ambient
air pollutants of both commuters and residents in close proximity
to these roadways (Pant and Harrison, 2013). Various methodolo-
gies have been implemented to measure and characterize vehicular
emissions, including on-road, roadside, tunnel, and dynamometer
measurements (Kleeman et al., 2000; Kristensson et al., 2004; Ning
et al., 2007; Ban-Weiss et al., 2008; Kam et al., 2012a; Franco et al.,
2013). Chassis dynamometer studies capture direct tailpipe emis-
sions under controlled experimental conditions. However, these
measurements do not take into account non-tailpipe emissions,
which may contribute significantly to overall traffic-associated PM
concentrations (Thorpe and Harrison, 2008), particularly in light of
observed reductions in primary exhaust emissions (Bishop et al.,
2013; Hasheminassab et al., 2014). Very importantly, dynamom-
eter studies do not consider various urban atmospheric processes,
such as atmospheric dilution and photochemical transformation,
which may substantially change the physicochemical and oxidative
characteristics of the emitted particles (Charron and Harrison,
2003; Canagaratna et al., 2004). In addition, dynamometer
studies cannot replicate the entire in-use mixed vehicle fleet, as
they are conducted only on a sub-set of vehicles. While tunnel
studies account for a larger fraction of on-road vehicles and capture
both tailpipe and non-tailpipe emissions, results from these studies
may not be applicable to open roadways, where meteorological
tunnel environments (Ketzel and Berkowicz, 2004). Roadside
studies provide the opportunity to measure a more representative,
larger vehicle fleet under actual ambient conditions. However,
since the measurements are restricted to fixed sampling sites, they
may not take into account emissions in the whole target roadway.
More realistic estimates of on-road vehicular emissions under
actual atmospheric and driving conditions can be obtained through
on-road mobile platform measurements (Jamriska and Morawska,
2001; Abu-Allaban et al., 2003; Franco et al., 2013). This method-
ology is arguably more appropriate to estimate traffic emissions, as
it closely captures the emissions from exhaust, abrasion, and re-
suspension sources. It should be clarified that on-road PM sam-
pling followed in this paper is different from in-cabin measure-
ments, where the effect of vehicle characteristics, ventilation
settings, driving conditions, and air exchange rates may play a
significant role on in-vehicle levels of pollutants and how they
compare to the roadway levels (Zhu et al., 2007; Hudda et al., 2011).
In this study, time-integrated samples of on-road PM were
collected in three distinct arterial routes in Los Angeles: a major
freeway which is dominated by light-duty-vehicles (LDVs) (I-110),
another major freeway with a higher fraction of heavy-duty-
vehicles (HDVs) (I-710) and two major surface street roadways
(the Wilshire/Sunset boulevards). Furthermore, sampling was car-
ried out at an urban stationary reference site at the main campus of
the University of Southern California (USC) for comparison of PM
chemical components and its oxidative potential at urban ambient
levels. The current work is an expansion of an earlier study by Kam
et al. (2012a,b) which addressed chemical speciation and emission
factors of size-fractionated PM in the same roadways of Los
Angeles. The current study is unique in that we have characterized
the oxidative potential of PM collected on-road across these major
roadways. To the best of our knowledge, this is the first study
investigating the PM oxidative potential on-road and across major
roadways of Los Angeles, the results of which provide valuable
insights into commuters’ exposure to high concentrations of toxic
PM. The unique sampling set-up employing light-weight, battery
operated cascade impactors made it possible to conduct on-road
characterization of PM chemistry and toxicity in different
roadway environments. Each micro-environment was sampled for
an extended time period (ranging from 55 to 95 h total) to ensure
the collection of adequate PM mass loadings for the chemical and
oxidative potential measurements of the PM2.5, as discussed in the
following section. Oxidative potential of PM2.5 was quantified using
the dithiothreitol (DTT) assay and its association with different
chemical species was investigated. Results from this study were
further compared with previous on-road and roadside studies
conducted over the past decade in the Los Angeles Basin to evaluate
to what extent policies implemented on vehicular emis-
sionsdmainly on diesel trucksdhave been effective in reducing
PM toxicity and/or carbonaceous species and metals and trace el-
ements linked to traffic emissions.
104 F. Shirmohammadi et al. / Atmospheric Environment 148 (2017) 102e114
2. Methodology
2.1. Sampling campaign
Sampling was conducted in three distinct roadway environ-
ments in Los Angeles within non-rush hour periods (e.g. 10:00 a.m.
to 3:00 p.m.) from October 2014 to January 2015, and again from
November 2015 until January 2016. The sampling periods were
intentionally selected during the colder months of the year to
minimize, to the degree possible, the contribution of secondary
organic aerosols (SOA) to PM mass. SOA is a regional aerosol (thus
impacting all sampling environments to more or less the same
degree) and has also been associated with the generation of excess
ROS (Delfino et al., 2010a; McWhinney et al., 2013; Verma et al.,
2012). Recent studies in Los Angeles indicated that the contribu-
tion of SOA to PM concentration is lower by about 50e60% in colder
seasons (i.e. from October to February) compared to warmer sea-
sons (i.e. from March to September) (Heo et al., 2015, 2013;
Hasheminassab et al., 2013).
The sampling routes are presented in Fig. 1. I-110 is a heavily
trafficked freeway, which connects the Port of Los Angeles in the
south to Pasadena in the north in a 51-km route. A 13-km segment
Fig. 1. Map of sampling routes: I-110, I-710 and Wilshire/Sunset boulevards. The USC urban reference fixed site is also denote by a black star.
of the I-110 freeway, starting from its junction with US-101 freeway
all the way up north to Pasadena, is open only to LDVs, while the
rest of the freeway is open to both LDVs and HDVs. The other
freeway sampling environment, I-710, is a 43-km-running freeway
and serves as the main corridor to and from the Ports of Los Angeles
and Long Beach, with a higher fraction of HDVs in comparison to I-
110. The route on Wilshire and Sunset boulevards covers 48-km on
two major surface streets, connecting the coastal areas of Los
Angeles to the city center, with some of the heaviest traffic in this
megacity. Hourly-averaged number of vehicles were obtained from
vehicle detection stations (VDS) on each freeway from the freeway
performance measurement system (PeMS), operated by the Cali-
fornia Department of Transportation (CalTrans). The average
vehicle flow (both LDV and HDV) in I-110 and I-710 were
4583 ± 1325 and 3905 ± 1896 vehicles/hr during the sampling
periods and HDVs constituted about 3.6 ± 2.8% and 11.8 ± 6.0% of
the traffic composition in the aforementioned freeways, respec-
tively. Lastly, sampling was also carried out at the Particle Instru-
mentation Unit at the main campus of the University of Southern
California (USC) as the urban fixed reference site, referred to as
“USC”, which is located about 4 km southwest of downtown Los
Angeles and 150 m downwind of the I-110 freeway.
 F. Shirmohammadi et al. / Atmospheric Environment 148 (2017) 102e114
It should be noted that since only one mobile sampling platform
was available, sample collections at different micro-environments
were not performed concurrently. However, the meteorological
parameters (i.e. temperature, relative humidity and wind speed)
during the sampling campaign were relatively stable and compa-
rable within and between the studied micro-environments. Mete-
orological data were obtained from nearby air quality monitoring
sites operated by the South Coast Air Quality Management District
(SCAQMD) and are presented in Table 1. In general, ambient tem-
perature spanned a narrow range of 18.8e24.0  C in all the sampled
micro-environments. Relative humidity had a maximum of 56.3%
and a minimum of 26.7% with an average value of 40.9 ± 8.3% over
all sampling micro-environments during the study period. Average
wind speed at the SCAQMD's stations closest to the studied road-
ways was 4.7 ± 0.4 mph, while it was relatively lower at USC
(2.6 ± 0.1 mph). The current study focuses on investigation of the
PM characteristics and in order to facilitate this, PM constituents
and toxicity as well as their association have been analyzed based
on the per PM mass data. The PM mass-based analysis also provides
direct insight on intrinsic properties of PM chemical composition
and relative toxicity. The volumetric concentrations (per m3 of air)
of chemical species are also presented in the Supplementary
Information.
2.2. Sampling instrumentation
The on-road sampling was performed with a 2014 Toyota Prius C
hybrid car equipped with six battery-operated Leland Legacy
pumps (SKC Inc., Eighty-Four, PA). This set up was identical to that
deployed in a previous study by Kam et al. (2012a,b) in which the
on-road size-segregated PM composition and emission factors
were investigated. In this set up, each pump was connected to a
Sioutas Personal Cascade Impactor Sampler (PCIS) (SKC Inc., Eighty-
Four, PA) and the flow rate for each PCIS was set to 9 lpm (Misra
et al., 2002). Roadway air was drawn into the PCIS units through
a curved stainless steel inlet with an inner diameter of 0.95 cm with
a total flow rate of 54 lpm (6 PCIS units each operating at 9 lpm).
The inlet was designed with a 90 -bend resulting in a 50% cut point
of about 10 mm (Peters and Leith, 2004), directing roadway air into
the vehicle window to a manifold with six branches each connected
to one PCIS. Because each pump operated at relatively moderate
flow rate of 9 lpm, prolonged sampling periods were necessary in
each micro-environment to reach sufficient PM mass loading for
the chemical speciation and toxicity analyses. More details of the
isokinetic sampling and instrumentation can be found in previous
study (Kam et al., 2012a). Over the entire campaign, five sets of
surface street (Wilshire/Sunset) samples were collected repre-
senting a total of 60 h of sampling. Three sets of samples were
collected on each freeway, with total sampling periods of 95 and
55 h for I-110 and I-710, respectively. Two sets of samples were
collected at the USC site for 55 h and sampling took place during
the times that corresponded to the freeways and surface streets
sampling periods.
Each PCIS unit was equipped with one impaction stage with 50%
cut-point of 2.5 mm to collect coarse PM, followed by an after-filter
Table 1
Summary of the average PM2.5 mass concentration (mg/m3) and meteorological data (±standard deviation) in the four sampled environments. The meteorological data were
obtained from the nearby air quality monitoring sites operated by the South Coast Air Quality Management District (SCAQMD).
Environment PM2.5 concentration (mg/m3)
Wilshire/Sunset 40.4 ± 12.6
I-110 15.9 ± 8.7
I-710 25.5 ± 8.8
USC 19.4 ± 3.2
105
stage to collect PM2.5. For the purpose of chemical speciation three
PCIS units were loaded with 37-mm PTFE (Teflon) filters (Pall Life
Sciences, 2-mm pore, Ann Arbor, MI) as the after-filter and 25-mm
Zefluor-supported PTFE filters (Pall Life Sciences, 0.5-mm pore,
Ann Arbor, MI) as the impaction substrates. The remaining three
PCIS units were loaded with 25-mm and 37-mm quartz filters
(Whatman International Ltd, Maidstone, England) as impaction
substrates and after-filter, respectively. The quartz filters were
prebaked at 550  C for 12 h and stored in baked aluminum foil prior
to sampling.
2.3. Gravimetric and chemical analyses
Samples from each set were analyzed to quantify PM2.5 mass
concentrations and its chemical constituents. Gravimetric mass
concentrations were determined by pre- and post-weighing the
Teflon and Zefluor filters, using a high precision (±0.001 mg) mi-
crobalance (MT5, Mettler Toledo Inc., Columbus, OH), after equili-
bration under controlled temperature (22e24  C) and relative
humidity (40e50%). Elemental and organic carbon (EC and OC)
content were quantified by analyzing a 1 cm2 punch of the quartz
filters using the National Institute for Occupational Safety and
Health (NIOSH) Thermal Optical Transmission (TOT) method (Birch
and Cary, 1996). For the organic speciation analysis only polycyclic
aromatic hydrocarbons (PAHs) were measured with gas chroma-
tography mass spectrometry (GC/MS) from the quartz filters
(Schauer et al., 1999). To measure the total elemental composition
of the PM, a section of the Teflon filter was digested in a mixture of
1.00 mL of 16 M nitric acid, 0.25 mL of 12 M hydrochloric acid and
0.10 mL of hydrofluoric acid using a microwave-aided (Milestone
Ethosþ) sealed Teflon bomb solubilization protocol. The digests
were then analyzed for 50 elements using a high resolution
(magnetic sector) inductively coupled plasma mass spectrometer
(SF-ICPMS, Thermo-Finnigan Element 2).
2.4. Toxicological analysis
The dithiothreitol (DTT) assay is commonly used to measure the
oxidative potential of PM in a cell-free construct in which DTT acts
as a surrogate of the biological reducing agent nicotinamide
adenine dinucleotide (NADH) and nicotinamide adenine dinucle-
otide phosphate (NADPH) (Kumagai et al., 2002, 1997). The ability
of a PM sample to catalyze the transfer of electrons from DTT to
oxygen by generating superoxide radical anions is measured in this
assay (Verma et al., 2014; Charrier et al., 2015). The concentration of
redox-active species in any given sample determines the rate of
depletion of DTT (nmol min1) under a standardized set of condi-
tions (i.e. 100 mM DTT, temperature 37  C and pH 7.4). The filters for
DTT assay were extracted in deionized water (DI, Milli-Q; > 18 M)
with sonication in a water bath for 60 min. The unfiltered extracts
were assayed for the DTT activity using an automated instrument
(Fang et al., 2015b). At designated time intervals (3, 11, 19, 27,
35 min), the remaining DTT in the incubation mixture was
measured and plotted against time to calculate the rate of DTT
consumption. The rate of DTT oxidation was then normalized to the
Temperature ( C) RH (%) Wind speed (mph)
24.0 ± 0.2 49.2 ± 0.7 4.5 ± 0.2
18.8 ± 0.6 29.4 ± 0.5 5.1 ± 0.5
21.7 ± 0.4 41.8 ± 3.2 4.4 ± 0.1
21.9 ± 0.4 43.3 ± 0.9 2.6 ± 0.1
106 F. Shirmohammadi et al. / Atmospheric Environment 148 (2017) 102e114
PM mass in the incubation vial to determine the DTT activity. The
methodological details of this assay can be found elsewhere (Cho
et al., 2005).
3. Results and discussion
3.1. PM2.5 mass concentrations and chemical composition
Table 1 presents the average PM2.5 mass concentrations for all
the sampled sets in each micro-environment. Average PM2.5 mass
concentrations on freeways were 15.9 ± 8.7 and 25.5 ± 8.8 mg/m3 in
I-110 and I-710, respectively. The Wilshire/Sunset boulevards, one
of the highly trafficked major surface streets of Los Angeles,
exhibited the highest PM2.5 concentration of the sampled roadways
with an average concentration of 40.4 ± 12.6 mg/m3, while the
average concentration at the USC reference site was 19.4 ± 3.2 mg/
m3.
3.1.1. Elemental carbon (EC) and organic carbon (OC)
Fig. 2 shows the average mass fractions (mg/mg PM) of elemental
carbon (EC) and organic carbon (OC) in each micro-environment.
Overall, I-110 exhibited the highest mass fractions of OC and EC
(0.37 ± 0.07 and 0.13 ± 0.04 mg/mg PM, respectively), while Wil-
shire/Sunset and USC roadways had the lowest mass fractions of OC
and EC. The mass fractions of OC in Wilshire/Sunset and USC were
comparable and approximately 40% lower than the level observed
in I-110. Overall, mass fraction of OC on both freeways was on
average 1.5 times greater than values obtained at Wilshire/Sunset
and USC. The volumetric OC concentrations spanned a range of
2.22e5.89 mg/m3 between all four environments and showed the
highest concentration in I-710, followed by I-110, Wilshire/Sunset
and USC site, as presented in Table S1. For EC, an indicator of
vehicular emissions especially from diesel trucks (Schauer, 2003),
the I-710 and I-110 mass fractions were comparable (0.12 ± 0.02
and 0.13 ± 0.04 mg/mg PM, respectively) and on average was 3.6 and
2.1 times higher than the Wilshire/Sunset and USC, respectively.
Although Wilshire/Sunset boulevards are highly trafficked surface
streets, their low levels of EC can be explained by their negligible
HDV volume. Higher EC levels on freeways are indicative of sig-
nificant contribution of vehicular emissions (with higher fraction of
HDVs) in these roadways. Similarly to OC, EC concentration also
showed highest levels in the I-710 (2.42 ± 1.17 mg/m3) followed by I-
Fig. 2. Mass fraction (mg/mg PM) of EC and OC in PM2.5 size range in the sampling
environments. Error bars correspond to standard deviation.
110 (1.48 ± 0.51 mg/m3) (Table S1).
3.1.2. Polycyclic aromatic hydrocarbons (PAHs)
PAHs are common products of incomplete combustion
(Manchester-Neesvig et al., 2003) and motor vehicles have been
identified as significant sources contributing to PAHs in the atmo-
sphere, originating primarily from unburned fuel, lubricating oil
and pyro-synthesis from lower molecular weight aromatics (Marr
et al., 1999). In the Los Angeles urban area, gasoline- and diesel-
fueled vehicles, as well as biomass burning are the major sources
of ambient PAHs (Polidori et al., 2008). Their concentration and
composition, however, may vary significantly, driven by factors
such as atmospheric conditions, source strength, gas-particle par-
titioning, and deposition processes (Polidori et al., 2008). The PAHs
discussed in this study included: phenanthrene, fluoranthene,
acephenanthrylene, pyrene benzo(ghi)fluoranthene, benzo(a)
anthracene, Chrysene, benzo(b)fluoranthene, benzo(k)fluo-
ranthene, benzo(j)fluoranthene, benzo(e)pyrene, benzo(a)pyrene,
indeno(1,2,3-cd)pyrene, benzo(ghi)perylene and coronene. Fig. 3
illustrates concentrations of the measured PAHs per PM mass in
the sampled roadways as well as at the USC reference site. The
cumulative mass fractions of measured PAHs were substantially
higher on the freeways than in other environments. The average
cumulative mass fraction of PAHs on both freeways were 3 and 3.3-
fold greater than the Wilshire/Sunset and USC levels, respectively.
The I-110 and I-710 exhibited levels of 0.16 ± 0.01 and
0.15 ± 0.01 ng/mg PM, respectively. The higher mass fraction of PAHs
on freeways indicates the significant role of vehicular emissions in
these environments. Several studies which have apportioned PAHs
emission factors (mg of pollutant per kg of fuel burned) for HDVs
and LDVs through tunnel studies (Phuleria et al., 2006) and dyna-
mometer studies (Schauer et al., 2002, 1999) have found that HDVs
can emit up to 50 times higher levels of PAHs than LDVs. These
studies also demonstrated that HDVs have greater contributions to
low molecular weight (MW  228) PAHs while high molecular
weight PAHs (MW  276) can be emitted by both LDVs and HDVs
(i.e. benzo(a)pyrene, benzo(ghi)perylene and indeno (1, 2, 3-cd)
pyrene) with substantially higher amounts from LDVs. The sum of
mass fractions of the aforementioned PAHs (i.e. benzo(a)pyrene,
benzo(ghi)perylene and indeno(1, 2, 3-cd) pyrene) was about 3.8
times higher in I-110 than I-710. Similar trend was also observed in
the volumetric PAHs concentrations in the sampled micro-
environments with highest levels on freeways (3.51 ± 0.22 and
2.35 ± 0.13 ng/m3 in I-710 and I-110, respectively) and cumulative
levels ranging from 0.98 to 3.51 ng/m3, as presented in Table S1.
3.1.3. Metals and trace elements
Fig. 4a illustrates the PM2.5 mass fraction of metals and elements
measured in the four roadway environments. S, Al, Ca, Fe, and Na
were the dominant species in all the sampled environments. The
concentrations of certain metals, including As, Cd, Cu, Ni, V and Zn,
were higher in the freeways than in the Wilshire/Sunset boulevards
and the USC site. These metals originate primarily from fuel com-
bustion and lube oil emissions (Geller et al., 2006; Schauer et al.,
2006; Lough et al., 2005; Sternbeck et al., 2002). Copper is also
reported to be present in brake wear emissions while tire wear has
been reported to be a significant source of Zn as well (Thorpe and
Harrison, 2008; Pant and Harrison, 2013). Higher levels of these
metals in the roadway environment, especially in the I-110 and I-
710 freeways are indicative of traffic as their primary source of
emission. The elements shown in Fig. 4a were further segregated by
their common sources and grouped as tracers of re-suspension of
soil and road dust (i.e. sum of Al, Ca, Mg and Ti) and vehicular
abrasion (i.e. sum of Ba, Cr, Cu, Mn, Ni, Pb, Sb and Zn) (Thorpe and
Harrison, 2008), as depicted in Fig. 4b. Road dust, of which crustal
 F. Shirmohammadi et al. / Atmospheric Environment 148 (2017) 102e114 107

Fig. 3. Mass fraction (ng/mg PM) of polycyclic aromatic hydrocarbon (PAHs) in PM2.5 size range in the sampling environments.

Fig. 4. (a, b). a) Mass fraction (ng/mg PM) of metals and trace elements, and: b) sum of metals and elements in groups in the sampled environments in PM2.5 size range. Sum of soil/
P P
road dust resuspension tracers: Al, Ca, Mg and Ti and sum of vehicular abrasion tracers: Ba, Cr, Cu, Mn, Ni, Pb, Sb and Zn. Error bars correspond to standard deviation. Cr at USC
site was below detection limit.
108 F. Shirmohammadi et al. / Atmospheric Environment 148 (2017) 102e114

dust is a key component, derive from different sources including
traffic and mineral dust (Kupiainen et al., 2005; Tanner et al., 2008).
Brake wear, including abrasion of brake lining material and brake
discs is known to contribute to the airborne PM trace metal con-
centration as well (Wåhlin et al., 2006; Gietl et al., 2010; Pant and
Harrison, 2013). The sum of vehicular abrasion tracers was on
average 3.8 ± 0.8 and 2.9 ± 0.6 times higher on both freeways than
Wilshire/Sunset and USC, respectively. In contrast, the sum of Al,
Ca, Mg and Ti as common tracers of re-suspended soil and road dust
showed higher mass fractions on the two freeways by a factor of
1.8 ± 0.6 than surface streets, while it had comparable levels to USC
site. These metals can be re-suspended and contribute to aerosol
PM in roadways due to the turbulence caused by the passing traffic
(Lough et al., 2005; Thorpe and Harrison, 2008). Thorpe et al.
(2007) also reported a strong association between heavy-duty
traffic and re-suspension of soil and road dust in the UK. The
volumetric concentrations of metals and elements were overall
higher in roadways in comparison to USC reference site, particu-
larly those that are associated with vehicular abrasion, as presented
in Table S1.
3.2. DTT activity of PM2.5 in various microenvironments
The PM2.5 DTT activity of the four sampled micro-environments
is presented in Fig. 5. Similar to the chemical data, the rate of DTT
consumption (activity) is normalized by PM mass (expressed in
units of nmol/min mg PM). As evident from Fig. 5, the intrinsic DTT
activity of PM varied substantially among the sampled environ-
ments, and in line with the discussions of the previous sections, the
DTT activity was highest at the I-710 (32.35 ± 13.26 nmol/min mg
PM), followed by I-110, Wilshire/Sunset and USC site, with DTT
activity levels of 27.90 ± 8.51, 16.07 ± 3.17 and 14.33 ± 1.72 nmol/
min mg PM, respectively. The DTT activity on freeways (i.e. with an
average of 30.13 ± 3.15 nmol/min mg PM) was roughly 1.9 and 2.1
times greater than the values obtained at Wilshire/Sunset and USC,
respectively. The strong influence of freeways emissions is evident
in the pronounced difference between freeways DTT activity and
surface streets as well as USC site. Despite the higher airborne PM
mass concentrations at Wilshire/Sunset boulevards in comparison
to the two freeways, a 1.7e2 fold increase in the per PM mass-
normalized DTT activity levels on freeways indicated higher levels
of toxic content per unit mass of PM on freeways. The per m3 of air
DTT activity spanned a range of 0.02e0.04 nmol/min m3 in the
sampling micro-environments, with highest and lowest levels
observed in Wilshire/Sunset boulevards and USC site, respectively,
as presented in Table S1.
3.2.1. Correlation analysis between PM chemical species and DTT
activity
To investigate the association of DTT activity with PM2.5 chem-
ical composition, univariate correlation analysis was performed
between the mass-normalized DTT activity and the mass fractions
of the chemical species in the all sampled environments. Table 2
presents the Spearman correlation coefficients (R) for the univari-
ate correlation analysis. The species with high correlation (R > 0.60)
are highlighted in bold, and statistically significant values (P < 0.05)
are denoted by an asterisk. The PM2.5 DTT activity was correlated
with several elements which are commonly associated with tail-
pipe and non-tailpipe vehicular sources, including As, Ba, Cu, Sb, V
and Zn. Arsenic, Cu, V and Zn are emitted as a result of fuel com-
bustion and lube oil emissions while Ba, Cr, Cu, Mn, Ni, Sb as well as
Zn can also be emitted from vehicular abrasion processes especially
from brake and tire wear abrasion (Lough et al., 2005; Schauer et al.,
2006; Pant and Harrison, 2013). Moreover, the sum of vehicular
abrasion tracers (i.e. Ba, Cr, Cu, Mn, Ni, Pb, Sb and Zn) was highly
correlated with DTT activity as well (R ¼ 0.61). Calcium and Ti
which are mainly associated with re-suspension of soil and road
dust were moderately, yet statistically significantly, correlated
(R > 0.50) with DTT activity. The correlation of these metals and
elements with DTT activity confirms findings from previous studies
(Fang et al., 2015a; Verma et al., 2015, 2009). EC and OC were also
strongly correlated (R  0.70) with DTT activity. The correlation of
OC with DTT activity underlies the contribution of organic com-
pounds to the oxidative potential of ambient PM. Moreover, cor-
relation of EC with DTT activity also suggests vehicular tailpipe
emissions as one of the significant contributors to PM-induced
oxidative potential. The sum of mass fraction of all measured
PAHs, discussed in previous sections, was also correlated with DTT
activity (R ¼ 0.66). The association between DTT activity and
Table 2
Spearman correlation coefficients (R) between dithiothreitol (DTT) activity (nmol/
min mg PM) and mass fraction of chemical species in PM2.5. Bold numbers indicate
R > 0.60 and * denotes values with P < 0.05. Sum of vehicular abrasion tracers
include: Ba, Cr, Cu, Mn, Ni, Pb, Sb and Zn.

Species PM2.5 DTT activity

Na 0.05
Mg 0.26
Al 0.08
S 0.30
K 0.15
Ca 0.51*
Ti 0.54*
V 0.73*
Cr 0.05
Mn 0.53*
Fe 0.63*
Co 0.50*
Ni 0.22
Cu 0.65*
Zn 0.57*
As 0.52*
Sb 0.56*
Cd 0.70*
Ba 0.69*
Pb 0.59*
OC 0.70*
EC 0.76*
Sum of PAHs 0.66*
Fig. 5. Mass-normalized PM2.5 DTT activity (nmol/min mg PM) of the sampled envi-
Sum of vehicular abrasion tracers 0.61*
ronments. Error bars correspond to standard deviation.
 F. Shirmohammadi et al. / Atmospheric Environment 148 (2017) 102e114 109

organic compounds in this study is also consistent with previous
studies (Cho et al., 2005; Verma et al., 2012).
We acknowledge that despite its lower wintertime levels, SOA
may still have some contribution to the total OC and thus the PM
mass levels even in colder months, therefore its contribution to
overall PM toxicity measured in our study's environments cannot
be completely disregarded. Other possible sources, such as ship fuel
oil combustion may also contribute to certain chemical species
discussed above (e.g. V and some PAHs) that were correlated with
DTT activity. However, with the aid of mobile sampling platform
and choice of sampling periods, we attempted to minimize, to the
degree possible, such impacts and mainly focus on PM freshly
emitted from vehicles in the roadway environments in this study.
3.3. Comparison with previous on-road and roadside studies
To put our results in context with previous studies, the
measured mass fractions of carbonaceous species, PAHs, metals and
trace elements in the PM2.5 size fraction were compared to previous
on-road and roadside studies in the Los Angeles Basin. A summary
of these results is presented in Figs. 6e8, while airborne (i.e., per m3
of air volume) concentrations are also reported in Tables S3e4. Of
the published studies, only Kam et al. (2012a) conducted on-road
measurements (in 2011) and the remainder of the cited studies
performed stationary sampling on the edge of the freeways (dis-
tance range: 2.5e10 m away from the edge of the freeway) before
2007, when major regulations on vehicular emissions, particularly
on diesel trucks, came into effect. Detailed information on the
sampling period and methodology of each study is presented in
Table S2. Although the studies considered in this meta-analysis
were conducted intermittently in different years, comparison of
PM mass-normalized levels among different studies reduces the
potential differences in meteorological conditions and atmospheric
dilution.
Compared to Kam et al. (2012a), where identical sampling
methodology at the same roadway environments was applied in
2011, similar levels were observed in this study on I-710 for EC
(0.10 ± 0.01 vs 0.12 ± 0.02 mg/mg PM), OC (0.30 ± 0.06 vs
0.30 ± 0.07 mg/mg PM) and PAHs (0.15 ± 0.03 vs 0.15 ± 0.04 ng/mg
PM). On I-110, however, mass fractions of EC, OC and PAHs
increased by factors of about 2.6, 1.5 and 1.6, respectively, in this
study compared to the levels reported by Kam et al. (2012a).
Moreover, mass fractions of important groups of metals (e.g.
vehicular abrasion) showed comparable levels on both freeways
between these two on-road studies (Fig. 8a, b).
Comparison of the current on-road study results with previous
roadside measurements near I-710 (Ning et al., 2007; Phuleria et al.,
2007; Ntziachristos et al., 2007b), which has one the highest HDV
fraction of about 12% in the United States, revealed that the mass
fraction of EC, OC and PAHs (important tracers of exhaust emis-
sions) have overall decreased by 58 ± 16%, 43 ± 12%, and 47 ± 10%,
respectively. On I-110 freeway (which has a much smaller HDV
fraction)), while mass fraction of OC decreased by 32 ± 21%
compared to previous roadside studies conducted between 2004
and 2005 (Kuhn et al., 2007; Ning et al., 2007; Phuleria et al., 2007),
the levels of EC and PAHs did not change significantly. The reduc-
tion trends on I-710 are also in concert with another on-road study
on the same freeway conducted by Kozawa et al. (2014), which
reported a nearly 70% reduction in the fuel-based emission factors
of black carbon (BC) between 2009 and 2011. Although these
findings are based on rather limited number of samples in each
study, the reduction trends observed especially at the I-710 indicate
an overall effectiveness of major policies implemented on diesel
exhaust emissions over the past decade. These reductions have also

Fig. 6. (a, b). Comparison of reported mass fractions of PM2.5 EC, OC (mg/mg PM) and PAHs (ng/mg PM) with previous studies conducted on or near: a) I-110 and b) I-710 freeways in
Los Angeles. Kam et al. (2012a) conducted on-road measurements and the rest performed stationary sampling on the edge of freeways. Error bars correspond to one standard
deviation. 1: Kuhn et al., 2007, 2: Ning et al., 2007, 3: Phuleria et al., 2007, 4: Ntziachristos et al., 2007b and 5: Kam et al., 2012a.
110 F. Shirmohammadi et al. / Atmospheric Environment 148 (2017) 102e114

Fig. 7. (a, b). Comparison of reported mass fractions of PM2.5 metals and trace elements (ng/mg PM) with previous studies conducted on or near a) I-110, b) I-710. Kam et al. (2012a)
conducted on-road measurements and the rest performed stationary sampling on the edge of freeways. Error bars correspond to one standard deviation. 1: Kuhn et al., 2007, 2: Ning
et al., 2007, 3: Ntziachristos et al., 2007c and 4: Kam et al., 2012a.

P P
Fig. 8. (a, b). Comparison of the sum of soil/road dust (SRD) resuspension tracers and vehicular abrasion (VA) tracers (SRD: Al, Ca, Mg and Ti; VA: Ba, Cr, Cu, Mn, Ni, Pb, Sb and
Zn) with previous studies conducted inside or near on a) I-110 and b) I-710 freeways. Kam et al. (2012a) conducted on-road measurements and the rest performed stationary
sampling on the edge of freeways. Error bars correspond to one standard deviation. 1: Kuhn et al., 2007, 2: Ning et al., 2007, 3: Ntziachristos et al., 2007c and 4: Kam et al., 2012a.

been verified by other studies with somewhat more robust datasets
and various methodologies (Bishop et al., 2013; Hasheminassab
et al., 2014; McDonald et al., 2015; Su et al., 2016).
In contrast to the bulk and speciated organic outcomes, as it can
be seen from Fig. 7a, b, the mass fractions of certain metals and
elements such as Mn, Ni, Cu, Ba and Pb (important tracers of
vehicular abrasion) have increased by factors of 3.3 ± 2.1 and
2.7 ± 1.4 on I-110 and I-710, respectively, in the current on-road
study compared to previous roadside measurements conducted
in 2004e2006. Unlike the other elements, we observed a
decreasing trend in the vanadium mass fraction (47 ± 20% reduc-
tion) over the years in both freeways, which may be due to the use
of cleaner diesel fuels in recent years (Shafer et al., 2012; Liu et al.,
2015). Metals were also further classified into soil/road dust and
vehicular abrasion groups, as discussed in previous sections
(Fig. 8aeb). As can be seen, the mass-normalized concentrations of
non-tailpipe PM sources increased in this study compared to pre-
vious roadside measurements by factors of 6.0 ± 3.4 and 3.4 ± 0.8
on I-110 and I-710, respectively. These results, altogether, indicate
that while regulations have been effective in reducing tailpipe
 F. Shirmohammadi et al. / Atmospheric Environment 148 (2017) 102e114
emissions, non-tailpipe emissions remain an important traffic-
related source of PM in the Los Angeles Basin with an increasing
contribution to total PM mass over the past decade
(Shirmohammadi et al., 2015, 2016).
Historic data on PM oxidative potential is much more limited;
only Ntziachristos et al. (2007a) reported PM oxidative potential
(using the DTT assay) in the vicinity of I-110 freeway. There are no
other studies reporting on-road PM toxicity in Los Angeles, and as
noted before, investigating the oxidative potential of on-road PM in
Los Angeles is a major novelty of this study. Ntziachristos et al.
(2007a) reported PM2.5 DTT activity values of 25.0 nmol/min mg
PM (based on a single measurement), 2.5 m away from the edge of
I-110 freeway. This value is generally consistent with the mass-
normalized DTT activity of 27.90 (±8.51) nmol/min mg PM
measured at the I-110 in the current study.
3.4. Comparison of measured DTT activity levels with previous
dynamometer studies
Previous dynamometer studies (Biswas et al., 2009; Cheung
et al., 2009; Geller et al., 2006) have investigated the associations
between PM components and redox activity based on the DTT assay
for different types of vehicles (i.e. gasoline/diesel, light duty/heavy
duty). Cheung et al. (2009) and Geller et al. (2006) have investi-
gated tailpipe emissions from different types of gasoline fueled
LDVs, while Biswas et al. (2009) studied exhaust emissions from
HDVs. To compare the DTT activity values obtained in this study
from on-road measurements to what would have been estimated
based on dynamometer measurements, the DTT activity of I-110
and I-710 freeways were reconstructed based on the aforemen-
tioned dynamometer studies as follows. The traffic composition
(i.e. the fraction of LDVs and HDVs) and total number of vehicles
were obtained from PeMS using the hourly-averaged number of
vehicles for each freeway during the sampling period. On average,
HDVs constituted 3.6 ± 2.8% and 11.8 ± 6.0% of the total traffic flow
in I-110 and I-710 freeways, respectively. Therefore, in order to re-
construct the DTT activity based on previous dynamometer studies
on HDVs, it was assumed that all HDVs on these freeways were
equipped with retrofitted technologies.
Per- PM mass DTT activity values are shown in Table S5 for
different types of vehicles with implemented control technologies,
which were obtained from the studies of Geller et al. (2006), Biswas
et al. (2009), and Cheung et al. (2009). Gasoline powered LDVs had
generally lower DTT activity, ranging from 12.0 ± 1.0 (Cheung et al.,
2009) to 25.0 ± 30.0 nmol/min mg PM (Geller et al., 2006), in
comparison to HDVs (30.5 ± 26.3 nmol/min mg PM (Biswas et al.,
2009)). In order to estimate the DTT activity of PM based on the
dynamometer studies in I-110 and I-710 freeways, the following
equations were used:
DTT activity (nmol/min mg PM) in I-110 ¼ (LDV DTT activity (nmol/
min mg PM)  0.964) þ (HDV DTT activity (nmol/min mg
PM)  0.036 (1)
DTT activity (nmol/min mg PM) in I-710 ¼ (LDV DTT activity (nmol/
min mg PM)  0.882) þ (HDV DTT activity (nmol/min mg
PM)  0.118 (2)
To obtain the errors of the estimated DTT activity, a Monte Carlo
simulation was carried out. A range of 12.0e25.0 (nmol/min mg
PM) (Cheung et al., 2009; Geller et al., 2006) was used for DTT ac-
tivity of gasoline powered LDVs, while the HDV DTT activity
(30.5 ± 26.3 nmol/min mg PM) was obtained from Biswas et al.
(2009) (Table S5). Fig. 9 illustrates the comparison of the re-
constructed DTT activity of PM for I-110 and I-710 with those
111
Fig. 9. Comparison between the measured DTT activity (nmol/min mg PM) on the two
studied freeways with reconstructed DTT activity based on previous dynamometer
studies. Error bars correspond to standard deviation.
obtained from this study. The DTT activity of the on-road PM2.5
measurements reported in this study was higher than that esti-
mated from dynamometer studies by factors of 1.4 and 1.5 for I-710
and I-110 freeways, respectively. Mann-Whitney Rank Sum test
indicated that the difference between the DTT activity obtained by
the two methods approached significance (P ¼ 0.1) despite the
relatively small sample size (N ¼ 6). This quite pronounced differ-
ence is likely due to the additional contribution of non-tailpipe
emissions to the overall PM2.5 DTT activity in this study's sampled
environments compared to dynamometer studies. The role of non-
tailpipe emissions on the oxidative potential of PM2.5 is also re-
flected by the high correlation of DTT activity with several
elemental tracers of re-suspended road dust and vehicular abrasion
(Table 2) as previously discussed.
4. Summary and conclusions
In this study, we deployed a mobile sampling platform to
investigate on-road chemical speciation and oxidative potential of
PM collected at different roadways of Los Angeles. To the best of our
knowledge, this is the first study investigating PM oxidative po-
tential on-road and across major roadways of this megacity. The on-
road PM sampling enabled us to characterize both vehicle tailpipe
and non-tailpipe emissions and the degree to which they influence
PM toxicity. The unique sampling set up allowed us to investigate
the traffic PM emissions inside major roadways where a substantial
portion of PM exposure occurs during commute, as well as in res-
idential communities in proximity of major roadways. Higher levels
of EC, OC, PAHs and metals and elements as well as oxidative po-
tential (measured by the DTT assay) were observed on freeways in
comparison to surface streets and the urban stationary reference
site at USC, demonstrating the significant role of vehicular emis-
sions to the overall toxicity of ambient PM. The mass fractions of EC
and OC on freeways were about 2.1 and 1.5 times higher than USC
site, respectively, while the sum of PAHs mass fractions on freeways
were 3.3-fold greater than USC site. The sum of mass fractions of Ba,
Cr, Cu, Mn, Ni, Pb, Sb and Zn that are common tracers of vehicular
abrasion emissions were 2.9 ± 0.6 times higher on freeways than
USC site, illustrating the importance of non-tailpipe emissions on
the overall PM levels. The PM2.5 DTT activity measured on both
freeways (30.13 ± 3.15 nmol/min mg PM, averaged over I-110 and I-
710) was roughly 2.1 times greater than the USC urban stationary
112 F. Shirmohammadi et al. / Atmospheric Environment 148 (2017) 102e114
reference site.
A comparison with previous on-road and roadside studies
suggested an overall reduction in mass fractions of EC, OC and PAHs
on freeways, most notably at the I-710, which is impacted by heavy
diesel truck traffic. These reductions are likely attributed to strin-
gent policies on vehicular exhaust emissions implemented by the
state of California (California Code of Regulations (2008)), which
make the contribution of non-tailpipe emissions to PM mass
increasingly more important, as evidenced by our results. The
impact of non-tailpipe emissions on PM-induced oxidative poten-
tial was further demonstrated by comparing the DTT activity
measured in previous dynamometer studies with that reported on
the freeway environments of this study. The approximately
1.4e1.5-fold higher DTT activity values measured on freeways than
the reconstructed values based on previous dynamometer studies
are mainly attributed to the redox activity of PM from non-tailpipe
emissions, and are further corroborated by the strong correlations
between DTT activity and mass fractions of PM species that are
tracers of vehicular abrasion.
Acknowledgements
The present project was supported by grant numbers
4R01AI065617-16 from the National Institute of Allergy and Infec-
tious Disease (NIAID), and 1R01ES024936-01 from the National
Institute of Environmental Health Sciences, U.S. National Institutes
of Health (NIH). The authors wish to thank the staff of the Wis-
consin State Laboratory of Hygiene (WSLH) for their assistance with
the chemical analysis. We also acknowledge the support of Uni-
versity of Southern California Provost PhD fellowship.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.atmosenv.2016.10.042.
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