ATMOSPHERIC ENVIRONMENT: X 6 (2020) 100070

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Atmospheric Environment: X
journal homepage: http://www.journals.elsevier.com/atmospheric-environment-x

Assessment of particulate toxic metals at an Environmental

Justice community
Olivia S. Ryder a, *, Jennifer L. DeWinter a, Steven G. Brown a, Keith Hoffman b, Betsy Frey b,
Ali Mirzakhalili b, 1
a
Sonoma Technology, Inc. (STI), 1450 N. McDowell Blvd., Suite 200, Petaluma, CA, 94954, USA
b
Department of Natural Resources and Environmental Control Delaware (DNREC), 100 W. Water Street, Suite 6A, Dover, DE, 19904, USA

A R T I C L E I N F O A B S T R A C T

Keywords: Exposure to particulate matter containing toxic metal species can have negative health implications. The com­
Toxic metals munity of Eden Park, Delaware, is surrounded by numerous industrial facilities, the Port of Wilmington, and a
Air quality highly trafficked freeway, all of which can be sources of toxic metals. The U.S. Environmental Protection
Positive matrix factorization
Agency’s EJ Screen ranks the community in the 88th percentile nationally for the Environmental Justice (EJ)
Community air monitoring
index of cancer risk and the 90th percentile for the EJ index of PM2.5 exposure. To understand the ambient
Environmental justice
Wilmington Delaware concentrations and sources of toxic metals and particulate matter, we collected hourly PM10 metals measure­
ments using an Xact 625i at a temporary monitoring site in the community. Additionally, PM2.5, wind speed and
direction, NOx, SO2, and black carbon were monitored. Conditional bivariate probability function maps and time
variation maps were constructed using the OpenAir statistical analysis package, and EPA Positive Matrix
Factorization was used to determine the sources of the measured metals. We found that transient concentration
events, where arsenic and lead concentrations were more than an order of magnitude larger than the study
average, occurred intermittently, but concentrations were generally below health benchmarks. Chromium and
nickel had common sources, including a metal plating facility and a chemical additive facility, and unidentified
sources were responsible for spikes in chromium levels up to 17 times above average. With Positive Matrix
Factorization, three sources were identified: soil/dust, concrete manufacturing dust, and brake wear. During
periods of moderate air quality (PM10 ¼ 55–154 μg/m3) concrete dust contributes 32% to PM10 concentrations,
while soil dust contributes 12%. Overall, the local industry and intermodal traffic emissions are large contrib­
utors to the ambient air pollution in the community, though transient high-concentration events from other
sources are also present.

1. Introduction Environmental Protection Agency (EPA) (Environmental Protec, 2018a,

2018b).
Metals can cause adverse impacts on the environment and human
health (Jaishankar et al., 2014; Tchounwou et al., 2012). Common
sources include industrial emissions, mobile source emissions, and
soil/dust. Anthropogenic metal sources include combustion of heavy oil
(e.g., vanadium and nickel), industrial facility emissions (e.g., arsenic
and lead), and mobile sources (e.g., iron and aluminum), among others
(Becagli et al., 2012; Brown et al., 2007; Hays et al., 2011; Miller et al.,
2007). Of the metals and metalloids present in PM10, antimony, arsenic,
beryllium, cadmium, chromium, lead, manganese, mercury, nickel, se­
lenium, and uranium have specific risk thresholds determined by the
� Arsenic is most commonly used as a wood preservative and in pes­
ticides, and it is found in soil. Industrially, arsenic is used to make
metal alloys for automobile batteries, semiconductors, and light
emitting diodes; inhalation exposure has been linked to lung cancer
(Tchounwou et al., 2012; U.S, 2007a).
� Nickel is used to make metal alloys for automobile batteries, semi­
conductors, and light-emitting diodes. Nickel may be released into
the air from industrial furnace stack emissions or from coal and oil
combustion. It is also found at low levels in soil and plants. Prolonged

* Corresponding author.
E-mail address: oryder@sonomatech.com (O.S. Ryder).
1
Present address: Oregon Department of Environmental Quality

https://doi.org/10.1016/j.aeaoa.2020.100070
Received 20 September 2019; Received in revised form 24 January 2020; Accepted 23 February 2020
Available online 9 March 2020
2590-1621/© 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
O.S. Ryder et al.
exposure to high levels of nickel can produce adverse effects,
including reduced lung function, chronic bronchitis, and lung cancer
(U.S, 2007b).
� Chromium is found in soil, rocks, plants, and volcanic emissions (U.S,
2012a) and is emitted from industrial and other anthropogenic point
sources such as welding, chrome plating, cement production, and
coal combustion (Tchounwou et al., 2012; U.S, 2012a). Chronic
exposure has been linked to nasal septum atrophy and cancer (U.S,
2012a).
� Manganese is naturally found in food, rocks and soil, and is used in
products such as fertilizer, fireworks, and paints. Industrially, man­
ganese is used in steel production to improve steel strength (U.S,
2012b). Prolonged inhalation exposure to elevated levels of man­
ganese results in cognitive effects and permanent nervous system
damage (U.S, 2012b).
� Lead is released from production of lead compounds and alloys, or
from coal and oil burning. Health impacts of lead exposure have been
studied extensively, and the results of chronic exposure to lead range
from cerebrovascular disease and cardiovascular effects to repro­
ductive and neurological problems (U.S, 2007c).
Soil and dust containing various concentrations of metals can
become entrained by wind, but also via agitation by car tires on road­
ways or unpaved lots (Seinfeld and Pandis, 2006; Pant and Harrison,
2013). Vehicular emissions such as tire degradation and brake wear can
also be sources of metals (Grigoratos and Martini, 2015). For example,
Hays et al (2011) found, among others, barium, copper, and zinc asso­
ciated with tire and brake wear, and nickel and chromium associated
with components of engine metal alloys during a study near a North
Carolina interstate highway (Hays et al., 2011). In a review, Grigoratos
and Martini (2015) summarize numerous studies with a table of 20 trace
metals detected in brake wear dust (Grigoratos and Martini, 2015). In
addition to those mentioned in the Hays study, iron, titanium, and
manganese comprise large concentrations of brake dust emissions.
While efforts over the past decades have reduced particulate exhaust
emissions from cars and trucks, non-exhaust emissions have not been a
focus of control efforts and are thus increasingly becoming an important
source of particulate emissions on roadways (Adamiec et al., 2016; Reid
et al., 2016). These emissions are of particular importance in commu­
nities located near major roads (Sunyer et al., 2015; Edwards et al.,
1994; Hitchins et al., 2000; Finkelstein et al., 2004; Kim et al., 2004;
Kunzli et al., 2000; Baldauf et al., 2008).
Another source that is of concern in certain communities is concrete
dust from cement plants. Rovira et al (2011) found that particles origi­
nating from such dust contained elevated levels of copper, lead, and
manganese (Rovira et al., 2011). Additionally, due to the composition of
concrete, the dust has high calcium content, especially compared to soil.
Calcium is prevalent in the environment and is also found naturally in
the form of calcium carbonate, which can be converted to calcium oxide
through heating or other mechanical processes used in making concrete
and drywall (Oss and Padovani, 2002). In addition to the metals cited by
Rovira et al. as components of concrete dust, particulate emissions of
calcium can be released into the atmosphere as a result of concrete
manufacturing. Calcium may thus act as a fingerprint identifier for
concrete emissions (Lioy and Yu, 2009).
Given the ubiquitous nature of metal-containing particles and the
potential toxic effects of prolonged human exposure to them, under­
standing sources of metal-containing particles in the air is key. Trace
metals in particles tend to remain preserved during transport and may
act as fingerprints for a specific source (Phillips-Smith et al., 2017a). In
such cases, receptor modeling can be used to elucidate particle sources
(also referred to as factors). Positive matrix factorization (PMF) is a
receptor model that has been used in numerous previous studies for this
purpose (Brown et al, 2007, 2012; Hays et al., 2011; Jeong et al., 2019;
Phillips-Smith et al., 2017b; Kim et al., 2003; Song et al., 2001). For
example, Song et al. (2001) used PMF analysis on PM2.5 metals collected
2
Atmospheric Environment: X 6 (2020) 100070
at three different sites in the northeastern United States (Song et al.,
2001). The analysis revealed six common sources among the three sites,
including coal combustion characterized by sulfur and selenium pres­
ence, sea salt characterized by sodium and sulfur, and oil combustion
characterized by nickel and vanadium. Jeong et al (2019) compared
PM2.5 metals at two near-road sites, performing PMF analysis to eluci­
date the contributions of exhaust and non-exhaust emissions. They
found that 9–19% of emissions measured were from exhaust, 2–6% were
from brake wear, and 3–4% were from re-suspension of road dust (Jeong
et al., 2019). Brown et al. (2007) identified eight sources of PM2.5 from
three years of data collected in Phoenix, Arizona, including soil/dust,
mobile sources, and industrial sources (Brown et al., 2007).
The measurements described herein were taken at Eden Park in New
Castle County, Delaware (Fig. 1). Eden Park, located in Wilmington,
Delaware, is the most populous city in the state with a population of
>70,000 people. The community is in the 88th percentile nationally for
the Environmental Justice (EJ) index of cancer risk based on the Na­
tional Air Toxics Assessment (NATA), the 90th percentile for the EJ
index of PM2.5 exposure, and the 86th percentile for the EJ index of air
toxics respiratory hazard, and has a known issue with high concentra­
tions of PM10 (Environmental Protec, 2017). The EJ index was created
by EPA to assess the risk associated with environmental and human
health conditions on minority and low-income communities with the
aim of improving environmental protection and mitigating risk for all
populations. The EJ index, as described by EPA, “is a way of combining
demographic information with a single environmental indicator—such
as proximity to traffic—that can help identify communities that may
have a higher combination of environmental burdens and vulnerable
populations.” The community is surrounded by sources of toxic metals,
including the Port of Wilmington and industrial facilities that include
metal recycling and concrete manufacturing. This neighborhood is also
adjacent to Interstate 495, which has an annual average daily traffic
value of 116,416 vehicles (Terminal Ave. to South Wilmington limits)
(Delaware Department of Transportation, 2019). The aim of this study
was to assess the air quality in the community for toxic metals and other
pollutants, and to assess the contribution of both local and regional
sources to PM10 concentrations.
2. Materials and methods
2.1. Sampling site and metal measurements
Measurements took place between October 19, 2018, and December
12, 2018, in the Eden Park community at the intersection of Terminal
and Wilmington Avenues (the southeast corner of Eden Park) as shown
in Fig. 1. An Xact 625i Multi-Metals Monitoring System (Cooper Envi­
ronmental) was used to measure PM10 metals on an hourly basis. Higher
time resolution allows for data that can be paired with meteorological
conditions to derive a more detailed understanding of sources and var­
iances in time (Furger et al., 2017). The Xact 625i pulls ambient air into
an inlet at 16.7 L/min onto filter tape. After an hour of collection, the
tape is automatically analyzed via nondestructive x-ray fluorescence
(XRF) while the next sample is collected. Hourly concentration values
for each metal were compared to their respective minimum limit of
detection (MDL), as provided by the instrument manufacturer. Species
with measured concentrations below the MDL greater than 50% of the
time were omitted from subsequent analysis. The metals included in the
analysis and their frequency of measurement above MDL are shown in
Columns 1 and 2 of Table 1. In addition to Xact sampling, aerosols were
also collected onto filters using a Thermo Partisol 2025 with a PM10 inlet
for a 24-h period every third day. The filters were analyzed by DNREC
for metals via XRF with EPA Method IO 3.3.
2.2. Gas and particle phase measurements
Hourly NO–NO2-NOx and trace level SO2 were measured using TAPI
O.S. Ryder et al.
Fig. 1. Satellite image of Eden Park and the surrounding area. Inset is a wind rose plot for Eden Park between October 19 and December 12, 2018.
T200U and Thermo 43i-TLE continuous gas analyzers. Black carbon
(BC) was monitored with a Magee Scientific Aethalometer 633, and
PM2.5 was measured using a TAPI T640 continuous particle monitor.
Wind speed and direction were measured using a Vaisala WXT-520 in­
strument. The data were reported at 60-min averages and wirelessly
transmitted to a data logger, where they were quality-assured weekly.
2.3. Data analysis
2.3.1. Individual metals
Analysis began with investigations of individual metals. Here, the
OpenAir R package was used to elucidate diurnal trends and generate
pollution rose plots and conditional bivariate probability function
(CBPF) plots. Diurnal profiles were generated using the time variation
function within OpenAir. This analysis produces average diurnal plots
for each day of the week, an average daily diurnal profile, and plots of
the average concentration on a day-of-the-week and monthly basis.
Pollution rose plots are a variation on wind rose plots, except the color
bar represents species concentration rather than wind speed. Some­
times, high concentrations of species which arise under low wind fre­
quency conditions are difficult to elucidate with pollution rose plots
alone. CBPF plots can be used to provide an additional view of the data.
CBPF plots are heat maps showing the probability that the concentration
of a species will be greater than some specified value for a given wind
direction and speed. On these plots, warmer colors represent higher
concentrations, and the location on the plot indicates the direction and
wind speed under which the high concentration occur. In comparison to
conditional polar plots, CBPF plots provide additional insight into the
wind speed and direction dependency of a species’ concentration. As
reported by Uria-Tellaetxe and Carslaw, CBPF is defined as:
3
Atmospheric Environment: X 6 (2020) 100070
mΔθ;Δu jC�x
CBPFΔθΔu ¼
nΔθ;Δu
Where mΔθ;Δu is the number of samples in wind sector Δθ that have a
wind speed interval of Δu and whose concentration (CÞ is greater than
the threshold x. In the case of the plots shown here, we use the 90th
percentile. This is divided by nΔθ;Δu , the total number of samples within
the wind sector and speed interval.
Since both the Xact data and filter measurements have associated
uncertainties, in addition to linear fit analysis, Deming regression was
performed to compare the filter and Xact data. Xact measurements were
averaged to daily values, and the regression calculation was performed
using the Deming package in R. The standard error input for the filter
measurements was the experimental error value. The standard error
input for the Xact measurements was calculated using the equation
below. Since the MDL used was for hourly measurements rather than 24
h measurements, the estimation of standard error is a conservative upper
limit.
StandardErrorXact ¼ 0:1 � ½species�dailyaverage þ 0:5 � ½MDL�Hourly
2.3.2. Positive Matrix Factorization
EPA PMF version 5.0 was used to determine source factors of the Xact
and BC measurements. This method has been described elsewhere, but
briefly, the model accepts a data matrix of measured concentrations and
uncertainties for a given set of species and decomposes the data set into
factors (Norris et al., 2014; Paatero and Tapper, 1994). These factors
represent potential sources that then need to be interpreted by the user
as to what each factor represents, given additional information about the
measurements (e.g., wind direction, nearby industrial sources, diurnal
variability, etc.). Each data point has a user-specified uncertainty value.
Here we used the sum of squares of the species-specific limit of detection
O.S. Ryder et al. Atmospheric Environment: X 6 (2020) 100070

Table 1
Table of species measured with the Xact, detection limits, and the percentage of measurements above the minimum detection limit; data are sorted by this percentage.
Gray text indicates the species were above MDL less than 50% of the time. Column 4 shows the median concentration and interquartile range from the 55-day sampling
period of this work as measured with the Xact. Columns 5 and 6 show the median concentrations from the Xact and collocated filter measurements for the 17 days with
filter measurements. Columns 7–9 are the r2, slope, and intercept of the linear fit between the filter and Xact measurements. Columns 9–10 are the slope and intercept
determined through Deming regression analysis.
Species MDL Measurements Xact Xact, 17 days with Filter Filter vs. Xact
(60 > MDL (%) (Median filter measurement measurement
Linear Linear Linear fit Deming Deming
min), [IQR]), μg/ (Median [IQR]), μg/ (Median [IQR]),
fit r2 fit slope intercept regression regression
μg/m3 m3 m3 μg/m3
slope intercept

Ca 3.00 � 100 0.586 1.241 [1.426] 1.215 [0.922] 0.86 1.70 0.67 0.81 0.07
10¡4 [1.528]
Fe 1.70 � 100 0.405 0.690 [0.461] 0.796 [0.454] 0.75 1.16 0.18 0.74 0.04
10 4 [0.821]
Zn 6.70 � 100 0.021 0.025 [0.009] 0.020 [0.013] 0.85 1.01 0.00 1.06 0.00
10 5 [0.029]
S 3.16 � 100 0.380 0.420 [0.249] 0.498 [0.211] 0.96 1.29 0.19 1.03 0.07
10 3 [0.345]
K 1.17 � 100 0.107 0.155 [0.079] 0.196 [0.095] 0.68 1.12 0.05 0.84 0.01
10 3 [0.152]
Ti 1.60 � 99 0.026 0.049 [0.032] 0.044 [0.025] 0.77 1.72 0.02 1.06 0.00
10 4 [0.054]
As 6.30 � 96 0.001 0.001 [ 0.001] 0.001 [0.001] 0.87 1.09 0.00 1.73 0.00
10 5 [0.001]
Ba 3.90 � 94 0.015 0.023 [0.023] 0.0313 [0.028] 0.86 0.76 0.00 0.68 0.00
10 4 [0.029]
Br 1.00 � 94 0.002 0.002 [0.002] 0.002 [0.002] 0.96 1.27 0.00 1.20 0.00
10 4 [0.002]
Al 0.1 94 0.748 0.966 [0.794] 0.275 [0.183] 0.84 4.97 0.17 4.79 0.14
[0.851]
Cl 1.73 � 94 0.133 0.157 [0.364] 0.145 [0.417] 0.90 1.03 0.00 0.95 0.02
10 3 [0.343]
Mn 1.40 � 89 0.007 0.014 [0.015] 0.020 [0.015] 0.66 0.92 0.00 0.69 0.00
10 4 [0.018]
Ni 1.00 � 87 0.001 0.002 [0.001] 0.001 [0.001] 0.70 1.35 0.00 2.08 0.00
10 4 [0.002]
Cr 1.20 � 85 0.002 0.004 [0.005] 0.005 [0.002] 0.46 0.87 0.00 1.11 0.00
10 4 [0.005]
Cu 7.90 � 82 0.006 0.010 [0.008] 0.026 [0.025] 0.47 0.22 0.00 0.28 0.00
10 5 [0.011]
Si 0.178 78 0.358 1.228 [1.611] 1.219 [0.844] 0.84 1.93 0.91 0.86 0.09
[1.402]
Sb 5.20 � 55 0.006 0.007 [0.001] 0.001 [0.006] 0.06 0.22 0.10 0.02 0.01
10 3 [0.008]
Pb 1.30 � 53 0 [0.002] 0.002 [0.001] 0.003 [0.003] 0.90 0.68 0.00 0.68 0.00
10 4
Se 8.10 � 48 7.39 � 10-5 0 [0] 0 [0] 0.78 0.49 0.00 0.51 0.00
10 5 [0]
V 1.20 � 43 0 [0.001] 0 [0.001] 0.001 [0.001] 0.47 1.12 0.00 0.89 0.00
10 4
Ag 1.90 � 41 0.001 0.002 [0.001] 0.001 [0.002] 0.29 0.18 0.00 0.20 0.00
10 3 [0.003]
Sn 4.10 � 38 0.002 0.003 [0.001] 0.001 [0.002] 0.12 0.11 0.00 0.12 0.00
10 3 [0.006]
In 3.10 � 16 0 [0.002] 0.001 [0] 0 [0.002] 0.28 0.09 0.00 0.08 0.00
10 3
Cd 2.50 � 10 0 [0] 0 [0] 0 [0.001] 0.04 0.04 0.00 0.03 0.00
10 3
Co 1.40 � 3 0 [0] 0 [0] 0.002 [0.002] 0.02 0.01 0.00 0.00 0.00
10 4
P 5.20 � 2 0 [0] 0 [0] 0 [0] NA NA NA NA NA
10 3
Hg 1.20 � 1 0 [0] 0 [0] 0 [0] 0.01 0.04 0.00 0.74 0.04
10 4
Bi 1.30 � 1 0 [0] 0 [0] NA NA NA NA NA NA
10 4
Tl 1.20 � 0 0 [0] 0 [0] NA NA NA NA NA NA
10 4

(LODi ) and species- and sample-specific analytical uncertainty output by
the Xact (ai;j ):
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
U ¼ LOD2i þ a2i;j
Solutions ranging from three to five factors were considered. For the
purposes of the PMF calculation, data reported as 0 concentration in the
hourly metals data set were set to the minimum detection limit for the
metal divided by 2 (Norris et al., 2014; Brown et al., 2015). The corre­
sponding uncertainty value was set to 5/6 * MDL, as is typically done
during PMF analysis. While assessing PMF solutions, individual species
were removed to determine the sensitivity of the solutions. Any species
whose concentration was above the MDL less than half of the time was

4
O.S. Ryder et al.
not included. Additionally, species with a signal-to-noise ratio of 0, as
calculated in EPA PMF, were also removed. Of the remaining species, it
was found that inclusion of chlorine resulted in a factor that was
dominated by chlorine with few other elemental contributions. The
same effect was observed for both sulfur and bromine. Considering the
types of sources present in the region, factors dominated by these species
did not explain the variance of the metals. These species were therefore
not used in PMF, leaving 15 metal species and BC. The concentrations
and uncertainties of crustal species of aluminum, silicon, calcium, iron,
and titanium were adjusted to account for the oxide compounds ac­
cording to known oxide ratios (Simon et al., 2011; Chow et al., 2015).
Overall, 1148 samples were run with a random seed number to start the
analysis. Gaseous and meteorological data were not included in the
model input, but they were used to assess the PMF factors.
Boot strapping (BS), displacement (Disp) and bootstrapping
enhanced by displacement (BS-Disp) were run to assess the validity of
the results (Paatero et al., 2014; Brown et al., 2015). In BS, EPA PMF
randomly selects non-overlapping blocks of consecutive samples,
creating a new input file with the same dimensions as the original,
running PMF on the re-sampled data set, and mapping these new BS
factors to the original factors. In DISP, each data point in the profile
matrix is perturbed to determine an uncertainty estimate of rotational
ambiguity. BS-DISP combines these processes, by displacing the BS
resampled data. Taken together, all the approximations of rotationally
accessible spaces for randomly located solutions represent both the
random uncertainty and the rotational uncertainty for the modeled so­
lution to the complete data set (Brown et al., 2015).
2.3.3. Black carbon
The Magee Scientific AE33 Aethalometer was used to measure PM2.5
black carbon. The AE33 collects ambient aerosol onto a filter tape; every
5 min, the absorbance of the material deposited on the tape is measured
at seven wavelengths, ranging from 370 to 960 nm. The BC concentra­
tion is from the 880 nm channel. BC absorbs uniformly across all
wavelengths at which absorbance is measured, but brown carbon, which
is produced by combustion of wood or other biomass, absorbs primarily
in the lower wavelengths of the measured range (Park et al., 2006; Jeong
et al., 2004). A commonly used method is to assume that BC is only from
wood burning and fossil fuel combustion, so that the difference in
absorbance at the 470 nm and 960 nm wavelengths can be used to
calculate the quantity of BC from wood burning (BCwb) and fossil fuels
(BCff). For each hour of BC measurement, we used this method to
calculate BCwb and BCff. More information on these calculations can be
found in the accompanying supporting information.
2.3.4. Back trajectories
HYSPLIT back trajectory analysis was performed using the NOAA
HYSPLIT trajectory model to determine the origin of air masses where
spikes in arsenic and lead were observed (Stein et al., 2015). The model
was using NAM 12 km meteorological data at 50 m, 100 m, and 250 m
elevation in back trajectory mode for 6 h preceding the spike in arsenic
or lead.
2.4. Comparison to health benchmarks
The U.S. EPA has developed dose-assessment response benchmarks
for toxic metals. The report lists the long-term chronic inhalation
thresholds for non-carcinogenic and carcinogenic effects (Environ­
mental Protec, 2014a). The values for non-carcinogenic effects are the
levels above which sensitive populations may start experiencing adverse
health problems other than cancer, such as breathing difficulties. The
cancer data are unit risk estimate (URE) values in units of 1/(μg/m3).
Unit Risk Estimates can be transformed to 1-in-a-million cancer bench­
marks by inverting them and dividing by a million, indicating that if a
population of 1 million people is exposed to a certain concentration over
a 70-year lifetime, one or more people are expected to develop cancer as
5
Atmospheric Environment: X 6 (2020) 100070
a result (Environmental Protec, 2018a).
3. Results and discussion
3.1. Xact and filter sample comparison
Xact hourly data were averaged to 24 h and compared to the collo­
cated filter samples analyzed by XRF to check the Xact measurements.
The average concentration of species measured by the Xact over the
whole study (55 days) and over the days when corresponding filter
measurements were taken (17 days), as well as the averages from the
filter measurements, can be found in Table 1. Linear fit and Deming
regression statistics between Xact and filter data are also shown in
Table 1. For all species measured above MDL more than 50% of the time,
the average metal concentrations measured by Xact and XRF were not
significantly different from each other within the overlapping inter­
quartile ranges (IQR). All species, with the exception of antimony
(whose signal resembled noise), exhibited modest agreement. Calcium,
zinc, sulfur, arsenic, barium, bromine, chlorine, and lead had r2 values of
0.85 or above, indicating good agreement between the two methods.
Tremper et al (2018) compared results obtained with a CES XACT 625
with those measured using ICP-MS (Tremper et al., 2018). They stated
that differences between these two methods resulting in slopes that
deviate from unity could result from sampling temperature differences
or variable blank levels in filter paper. These may also be applicable in
this study. Additional error may have arisen from storage of 24-hr filter
samples for 1 month prior to chemical analysis, versus collection and
immediate analysis for 1-hr Xact samples in this work. It is also possible
that deviations in slope from unity may be attributable to differences in
instrument sensitivities. The analysis that follows utilizes the Xact data.
3.2. Wind and PM trends
The inset in Fig. 1 shows a wind rose plot illustrating the distribution
of winds at the Eden Park sampling site for the duration of the study,
October 18, 2018–December 12, 2018. During this time, winds from the
west dominated: winds originated from between 230� and 320� more
than 60% of the time. Over the course of the sampling period, hourly
PM2.5 varied between 0.6 μg/m3 and 42.2 μg/m3, with a mean value of
10.7 � 7.4 μg/m3 (1σ). PM2.5 concentrations peaked around 7:00 a.m.
and were lowest at approximately 6:00 p.m. Monday through Friday,
with little diurnal trend seen on the weekend. For the same time period,
hourly PM10 varied between 1.1 μg/m3 and 224.2 μg/m3, with a mean
value of 28.5 � 26.7 μg/m3 (1σ). On average, PM10 concentrations
reached a maximum between 7:00 a.m. and 11:00 a.m. and were highest
from Monday through Thursday, with lower concentrations on Friday
and no strong diurnal trend on the weekend. On an hourly basis, the sum
of all species measured by the Xact accounted for 21.1 � 6.3% (1σ) of
total PM10 mass on average, but varied over the course of the study to as
high as 80% and as low as 0.6%. Of the metal contribution to PM10, up to
5% was from metals both defined as EPA air toxics and measured above
their MDL over 50% of the time.
Figs. S1a and S1b show time series and diurnal profiles of NOx, BC,
and SO2 concentrations. Over the sampling period, the median SO2
concentrations were 0.60 ppb [IQR ¼ 0.50 ppb], NOx concentrations
were 20.3 ppb (IQR ¼ 21.7 ppb] and BC concentrations were 0.66 μg/m3
[IQR ¼ 0.95 μg/m3]. SO2 concentrations showed a diurnal profile with
multiple sharp peaks during the weekdays, typically occurring between
8:00 a.m. and 12:00 p.m. Monday through Thursday. On Friday through
Sunday, SO2 concentrations showed a less pronounced morning peak.
However, the median weekday vs. weekend concentrations of SO2
remained comparable (median weekday SO2 ¼ 0.60 ppb [IQR ¼ 0.50
ppb]; median weekend SO2 ¼ 0.60 [IQR ¼ 0.40 ppb]). On average, NOx
exhibited a strong diurnal profile, sharply peaking between 6:00 and
7:00 a.m. daily Monday through Thursday. Friday exhibited this same
profile, but the peak was less pronounced, and weekend trends did not
O.S. Ryder et al.
have a well-defined peak in concentration. This is consistent with high
commuter vehicle traffic during the mornings on weekdays (median
weekday NOx ¼ 22.3 ppb [IQR ¼ 22.8 ppb]) and less traffic on the
weekends, when fewer commuters are on the road (average weekend
NOx ¼ 14.95 ppb [IQR ¼ 15.75 ppb]). BC tracked NOx trends closely,
even during the weekends when a strong NOx diurnal pattern was not
present (average weekday BC ¼ 0.748 μg/m3 [IQR ¼ 1.103 μg/m3];
average weekend BC ¼ 0.483 μg/m3 [IQR ¼ 0.596 μg/m3]). Since BC is
also associated with vehicle emissions, the correlation with NOx is
expected.
3.3. Comparison to health benchmarks
Table 2 lists the toxic metals for which the EPA has developed a dose-
assessment response benchmark (Environmental Protec, 2014a) and
also lists the average concentrations and standard deviations from this
work (55-day average) for comparison. It should be noted that the
chronic inhalation benchmarks are for exposure over a 70-year lifetime,
while the concentrations reported from this work are for a much shorter
time scale. Health risk screening is typically employed to compare
concentrations to benchmarks in order to prioritize further analyses.
Despite the discrepancy in time scale, the concentration comparisons
here are performed as a screening to identify which compounds may be
of highest importance in the community for future focus.
The average arsenic concentration is above the cancer threshold (1
� 10 6 benchmark ¼ 0.00023 μg/m3) indicating an approximate cancer
risk of 7.3-in-a-million. Arsenic is far below the non-cancer threshold of
0.015 μg/m3.
Chromium concentrations at Eden Park have a mean of 0.0049 �
0.0084 μg/m3 (1σ), which falls below the Cr(III) non-cancer standard of
0.1 μg/m3. The chronic exposure cancer values are for Cr(VI), the more
toxic valence state form, and not Cr(III) (Environmental Protec, 2018a).
Though total chromium is measured at Eden Park, Cr(VI) can be esti­
mated as 0.0125 of total chromium, based on EPA guidance (McCarthy,
2018; Environmental Protec, 2018c). With this method, Cr(VI) at Eden
Park is estimated to be 6.13 � 10 6 μg/m3, which falls below the cancer
threshold (1 � 10 6 benchmark ¼ 8.3 � 10 5 μg/m3). We note that the
national Cr(VI) to total chromium ratio of 0.0125 may not be appro­
priate if the chromium is locally produced by sources such as chromium
plating, but the ratio of Cr(VI) to total chromium would have to be above
0.15 to exceed the 1 � 10 6 benchmark.
For lead, Eden Park mean concentrations were 0.0019 � 0.0053 μg/
m3 (1σ), which is below the non-cancer threshold and National Ambient
Air Quality Standard of 0.15 μg/m3 (Environmental Protec, 2016). For
nickel compounds, which have a non-cancer threshold of 0.09 μg/m3,
Table 2
Comparison of chronic inhalation benchmarks for non-cancerous effects (Col­
umn 2), the unit risk assessment benchmarks for cancerous effects (Column 3),
and the mean and 1σ values from this work (Column 4).
Species Chronic Inhalationa Study Period
Mean � 1σ
Non-Cancer Hazard Cancer 1-in-a-million This Work (μg/
Index (μg/m3) Benchmark (μg/m3) m3)
As 0.015 0.00023 0.0017 �
0.0026
Crb 0.1 8.3 � 10 5
0.0049 �
0.0084
Pb 0.15c – 0.0019 �
0.0053
Ni 0.09 – 0.0021 �
0.0037
Mn 0.3 – 0.0162 �
0.0267
a
Data from Dose-Response Assessment Tables, EPA.
b
Chronic inhalation values specific to Cr(VI).
c
NAAQS standard.
6
Atmospheric Environment: X 6 (2020) 100070
the Eden Park concentration (0.0021 � 0.0037 μg/m3 [1σ]) falls below
the benchmark. Manganese has a reported non-cancer inhalation
threshold of 0.3 μg/m3, which is well above the average value measured
at Eden Park (0.0162 � 0.0267 μg/m3 [1σ]).
3.4. Individual species analysis
Initially, the individual metal species were analyzed separately and
trends were compared to elucidate how metals were co-varying with
each other as well as with NOx, SO2, PM10, and BC. Fig. 2 shows a time
series of the 15 species used subsequently in the PMF analysis as well as
NOx and PM10. This section discusses trends in BC and in toxic species:
(1) chromium and nickel, (2) manganese, and (3) arsenic and lead. We
also discuss high-concentration species barium and copper, which trend
together, and calcium. Other species on the EPA air toxics list are not
discussed here, since their concentrations were below the minimum
detection limit more than 50% of the time. Pollution roses, CBPF plots,
and diurnal profiles for metals, calculated using the OpenAir R package
(Carslaw and Ropkins, 2012), can be found in Figures S2 through S12.
3.4.1. Black carbon
Over the course of the study, median BC concentrations from wood
burning (BCwb) were 0.12 μg/m3 (IQR ¼ 0.15 μg/m3), and BC concen­
trations from fossil fuel combustion (BCff) were 0.52 μg/m3 (IQR ¼ 0.81
μg/m3). This equates to BC contributions of 20 � 14% from biomass
burning and 80 � 14% from fossil fuel. Diurnal plots of BCwb and BCff
along with NOx are shown in Fig. S1b. The data show that BCff has a
strong morning peak that coincides with NOx, while BCwb exhibits
higher concentrations during the evening hours.
3.4.2. Chromium and nickel
Chromium concentrations during the study had a median value of
0.002 μg/m3 [IQR ¼ 0.005 μg/m3]. Concentrations were highest
Monday to Thursday and decreased slightly on Friday and Saturday,
with very low levels seen on Sunday. As was seen in other species, there
were periodic pulses in chromium concentration ranging from 1 to 2 h,
when chromium concentrations spiked up to 17 times the mean. These
spikes do not consistently correspond with spikes in other species such
as lead and arsenic, though chromium is moderately well correlated
with nickel (r2 ¼ 0.65). Chromium does not track with BC (r2 ¼ 0.07) or
NOx (r2 ¼ 0.07), indicating that the main source of chromium is not
likely related to traffic patterns. This is confirmed through CBPF anal­
ysis, which shows the greatest probability of high chromium concen­
trations when winds are above 4 m/s from the west-northwest (Fig. 3). A
nickel, cadmium, and chromium plating facility is 0.95 miles (1.5 km)
northwest of Eden Park and may contribute to the chromium and nickel
concentrations (Fig. 1). Concentrations are also high under low wind
speeds from the southeast, corresponding to the locations of I-495; fa­
cilities for soil treatment and recycling, where metals and non-metals are
separated; an oil pipeline storage facility; a chemical additive facility
supplying minerals for colorants, batteries, and specialty applications;
and a salt and packaged ice melt manufacturer. Some of these facilities
can handle chromium in various forms and may be the source of chro­
mium from the southeast.
Similar to chromium, nickel CBPF plot analysis indicates that high
concentrations predominantly occur with winds from the west-
northwest, with the highest concentrations being more likely when
winds are above 5 m/s (Fig. 3). As was the case with chromium, nickel
appears to have a second contributory source to the southeast. The Toxic
Release Inventory (Environmental Protec, 2018d) lists Prince Minerals,
a manufacturer of specialty chemicals and industrial additives to the
southeast, as a known contributor of manganese and nickel to the at­
mosphere. Collectively, there appear to be multiple, intermittent sources
of chromium and nickel, though as indicated by the moderate correla­
tion, the emissions of chromium and nickel may not always occur
coincidentally (Fig. 4A). In addition, part of the correlation may be due
O.S. Ryder et al.
Fig. 2. Time series of select species over the course of the sampling period at Eden Park. Units are μg/m3 unless otherwise stated on the y-axis. Red dashed lines
indicate the median value measured across the study period and are shown for context. (For interpretation of the references to color in this figure legend, the reader is
referred to the Web version of this article.)
to measurement biases. A comparison of nickel’s Xact measurements to
filter measurements was reasonable (r2 ¼ 0.70), but chromium showed
more scatter between the collocated measurements (r2 ¼ 0.46). Due to
the intermittent concentration spikes and combination of sources in the
area, the signal may not be sufficiently strong to extract a specific
chromium/nickel factor in PMF.
3.4.3. Manganese
Over the sampling period, the median manganese concentration was
0.007 μg/m3 [IQR ¼ 0.018 μg/m3]. The manganese time series (Fig. 2)
shows time periods (lasting between 1 and 12 h) of higher manganese
concentration spikes, which happen sporadically on weekdays. The
largest peak, occurring at 4:00 p.m. on November 6, 2018, is 13.7 times
larger than the mean (0.016 μg/m3). CBPF plots show that higher con­
centrations of manganese occur predominantly when wind speeds from
the northwest are more than 3 m/s. There is also a weaker source present
under lower wind speeds (<2 m/s) southeast of Eden Park, which could
possibly relate to the specialty chemical manufacturer mentioned above
for nickel (Fig. 3).
3.4.4. Arsenic and lead
Diurnal analysis of arsenic shows that this metal has very low con­
centrations (median ¼ 0.001 μg/m3, IQR ¼ 0.001 μg/m3) and no
consistent diurnal profile from day to day. CBPF plots indicate that high
concentrations are most probable under very low wind speeds (<1 m/s)
7
Atmospheric Environment: X 6 (2020) 100070
and are centralized directly at the sampling location (Fig. 3). While the
arsenic signal tends to remain low, there are intermittent spikes of very
high arsenic concentrations. There are twelve such instances of high
concentrations, and these events fall on Tuesdays, Wednesdays, Fridays,
Saturdays, or Sundays. The highest spikes are 0.044 μg/m3, occurring on
Sunday, November 11, at 4:00 p.m.; 0.034 μg/m3 on Saturday, October
20, at 6:00 p.m.; 0.030 μg/m3 on Wednesday, November 21, at 4:00 p.
m.; and 0.022 μg/m3 on Friday, November 23, at 10:00 p.m. They range
between 5 and 25 times larger than the mean arsenic concentration
(0.002 μg/m3) during the study. Since these spikes typically occur after
business hours, it is unlikely they are associated with an industrial
source. HYSPLIT back trajectory analysis performed for the 6 h prior to
the peak of each arsenic spike showed no consistent origin of winds at
50 m, 100 m, or 250 m elevation. To further investigate the spikes in
arsenic, pollution roses were created for each of the spikes, including 3 h
before and after the peak as a buffer. However, the pollution roses did
not show consistent trends in wind speed or direction that would help to
elucidate the source of the sudden increases in arsenic.
The CBPF plot for lead looks similar to that for arsenic (Fig. 3), where
the highest concentrations are more likely to be found directly at the site
under low wind conditions (<1 m/s). However, there also appear to be
additional locations where lead may be found. For example, higher
concentrations of lead are found when winds are from the northwest and
northeast. Again, like arsenic, lead has no diurnal structure and has very
low concentrations (median ¼ 0 μg/m3, IQR ¼ 0.002 μg/m3) throughout
O.S. Ryder et al. Atmospheric Environment: X 6 (2020) 100070

Fig. 3. Conditional bivariate probability function plots for species over the course of the study. The radial axis indicates wind speed in m/s, and the color bar
indicates the probability that a species will be greater than the 90th percentile. (For interpretation of the references to color in this figure legend, the reader is
referred to the Web version of this article.)

Fig. 4. Gray markers show chromium vs. nickel (left) and arsenic vs. black carbon from wood burning (right). Gray dashed lines are linear fits to data.

the study, except for sporadic times when the concentrations spike be­
tween 4 and 39 times above the mean value of 0.002 μg/m3. Here, lead
spikes appear sporadically throughout the week, and HYSPLIT back
trajectory analysis showed no consistent origin for the air masses leading
up to the spikes. Due to their similar CBPF maps and intermittent spiking
behavior, the lead and arsenic time series were compared to each other
as a determinant of how closely they may be related. 33% of the lead
spikes are unassociated with spikes in arsenic, 33% correspond with an
of wood treated with preservatives. To assess whether soil was respon­
sible for the spikes, the arsenic signal was compared with the signals of
potassium and BC. Since potassium has multiple environmental sources,
the signal was apportioned to crustal potassium and non-crustal potas­
sium using a literature-derived mass reconstruction equation, where
non-crustal potassium can be estimated as
Knon ¼ 1:2 � ðKtotal 0:6Fetotal Þ
crustal

increase in arsenic but below the 99th percentile value determined for
arsenic, and 33% of the lead spikes coincide with arsenic spikes. It is
clear that both species are typically low except for aberrant events of
unknown origin.
Two additional potential sources of arsenic are soil and local burning
(Simon et al., 2011; Chow et al., 2015). Crustal potassium was then
calculated as the difference between the total potassium signal and the
non-crustal potassium. Scatter plot analysis showed that the spikes in
arsenic were not correlated with high concentrations of crustal potas­
sium, indicating that soil is unlikely to be responsible for the increased

8
O.S. Ryder et al. Atmospheric Environment: X 6 (2020) 100070

levels of arsenic. 3.4.5. Barium and copper

To assess whether the arsenic spikes resulted from local burning
activities, the biomass burning contribution to BC was compared to
arsenic. This analysis showed the spikes were not correlated with high
concentrations of wood burning BC (Fig. 4B). Since the spikes are spo­
radic and do not correlate with either soil or wood burning, the two
likely local sources, the origin of the arsenic spikes remains unknown.
Barium and copper exhibit similar patterns to one another in their
concentration patterns and diurnal variability, correlating with an r2 of
0.77. The median concentration during the study was 0.015 μg/m3 (IQR
¼ 0.029 μg/m3) for barium and 0.006 μg/m3 (IQR ¼ 0.011 μg/m3) for
copper. There are sporadic periods of high concentrations of both spe­
cies lasting between 2 and 10 h throughout the week, including Sundays.
CBPF plots for both species show concentrations above the 90th
percentile when the winds are low at <1 m/s. They both exhibit diurnal

Fig. 5. PMF profiles for the 3-factor solution where bars are the concentration of each species, and the markers are the percentage of species and a time series trace
for each factor and PM10. Aluminum, silicon, calcium, iron, and titanium include adjustments for oxides.

9
O.S. Ryder et al.
variability, co-varying with NOx (Ba/Cu r2 ¼ 0.71; Cu/NOx r2 ¼ 0.58),
and have a morning and evening peak. Their concentrations are highest
Monday through Thursday, are lower on Friday, and are lowest on the
weekend. These trends suggest that copper and barium concentrations
relate to traffic patterns and vehicle activity. These species, along with
antimony and zinc, can be from vehicle brake wear, which would be
consistent with the high concentrations under low wind speed, diurnal
profiles, and trends with NOx observed here (Hays et al., 2011; Dillner
et al., 2005; Thorpe and Harrison, 2008; Lough et al., 2005; Hjortenk­
rans et al., 2007).
3.4.6. Calcium
The median calcium concentration was 0.586 μg/m3 (IQR ¼ 1.528
μg/m3) during the study. The greatest probability of high concentrations
(Fig. 3) was when winds were above 5 m/s from the west-northwest. On
weekdays, median calcium concentrations were 0.883 μg/m3 (IQR ¼
2.09 μg/m3); however, on the weekends, they were 4.5 times lower. The
average diurnal profile (see Fig. S5) indicates that calcium tracks PM10
(r2 ¼ 0.78) but not NOx (r2 ¼ 0.035) or BC (r2 ¼ 0.049). The reduced
calcium weekend signal and correlation with PM10 might be explained if
the source of the calcium is nearby cement facilities that run on a
Monday to Friday schedule only.
3.5. Positive Matrix Factorization analysis
In the PMF analysis, solutions ranging from 3 to 5 factors were
considered. A 5-factor solution appeared to over-fit the data, with two
highly correlated crustal factors (slope of 0.98 and an r2 value of 0.87).
The 4-factor solutions produced two factors related to crustal species
and two factors that correlate with BC. As in the 5-factor solution, the
two crustal factors co-varied, with a slope of 0.87 and an r2 value of 0.87.
This indicates that the 4-factor solution was likely also overfitting the
data. A 3-factor solution offered the most interpretable solution and was
reproducible, with crustal (Factor 1), calcium (Factor 2) and brake wear
(Factor 3) factors.
For BS, 400 runs were performed with a block size of 22 and mini­
mum correlation r2 value of 0.8. BS runs of the 3-factor solution showed
that 95% of the bootstrapped Factor 1 and 100% of the bootstrapped
Factors 2 and 3 mapped to the corresponding base factor. 0.5% of Factor
1 was unmapped. The BS results showed all species falling within the
interquartile range, zero cases with swaps, and a change in the sum-of-
squares object function (%dQ) of less than 0.1%. For BS-Disp, the active
species were set as iron, copper, and silicon, and the results showed zero
cases with swaps.
The details of the resultant factors are described below. PMF factor
profiles and time series are shown in Fig. 5. The amount of each indi­
vidual metal species and black carbon is shown in bars, while the per­
centage of each total species measured that contributes to each factor’s
total mass is shown by red markers. Summing the percentage values of a
species over all three factors equals 100%.
Factor 1 is dominated by aluminum, chromium, iron, manganese,
nickel, and titanium. While silicon is also present, the largest percent of
silicon is in Factor 2 rather than this factor. Factor 2 also contains strong
contributions from aluminum, chromium, manganese, nickel, and tita­
nium. Additionally, Factor 2 features high calcium and potassium
components and a lower contribution from iron. Upon initial compari­
son, these two factors appear similar, as they both contain crustal ele­
ments. The two factors have modest independence, with a slope of 0.56
and an r2 of 0.57. In order to distinguish the two potential sources, in­
formation on the composition of local soil was needed.
A recent laboratory analytical report of soil composition in the state
of Delaware contains data from two different soil types, Gleneig and
Neshaminy, from within 6 miles (9.7 km) north-northwest of Eden Park
(Galloway and Johnson, 2012). These data were used to generate ratios
of the elemental contents of the soil in the area for comparison to the
ratio of elements in PM measured in this work (Table 3). The soil was
10
Atmospheric Environment: X 6 (2020) 100070
Table 3
Ratios of aluminum, iron, potassium, and calcium to calcium calculated from
elemental concentrations reported for two types of soil less than 6 miles (9.7 km)
from Eden Park (Rows 1 and 2). Rows 3 and 4 show calculated elemental ratios
for Factors 1 and 2 from the PMF solution.
Data Al Fe K Ca
Gleneig Soil 12 16 1 1
Neshaminy Soil 17 18 1 1
Factor 1 14 12 0.2 1
Factor 2 0.5 0.2 0 1
sampled and tested in the laboratory via either Atomic Absorption or
Inductively Coupled Plasma Mass Spectrometry for elemental compo­
sition. While the ratios from Factors 1 and 2 do not match perfectly to
either soil type, Factor 1 ratios for each element are of the same order of
magnitude as both soil types. For Factor 2, in comparison, potassium
ratio values are one order of magnitude higher and calcium ratio values
are two orders of magnitude higher. This suggests that Factor 2 is not
crustal and may instead derive from local concrete manufacturing. The
most common type of concrete is portland cement, which typically
ranges between 60% and 70% CaO species (Oss and Padovani, 2002).
The four main mineral forms of CaO are SiO2⋅3CaO, SiO2⋅2CaO,
Al2O3⋅3CaO, and 4CaO⋅Al2O3⋅Fe2O3, which is consistent with contri­
butions of silicon, aluminum, and iron to Factor 2.
Further analysis was conducted by developing pollution roses and
CBPF plots for each factor, shown in Fig. 6. The CBPF plots show that
Factors 1 and 2 are highest when winds are from the west and northwest.
The highest probability of concentrations at or above the 90th percentile
for both Factors 1 and 2 occurs at wind speeds above 5 m/s, indicating
that both factors arise from sources farther away from Eden Park, and
that these factors impact the site only when winds are sufficient to
transport PM10 particles. The pollution rose plots (Fig. 6d and e,
respectively) also confirm the directionality of the source emissions and
show that the greatest concentrations for Factor 1 occur 20% of the time
from the west and 24% of the time from the west-northwest. Similarly,
24% of Factor 2 comes from the west.
The combined results indicate that Factor 1 is likely a local soil/dust
source. To the west and northwest of Eden Park is a large open dirt lot on
South Market Street used by construction vehicles, unpaved parking
areas used to house salvage vehicles, and parkland. All of these are
possible sources of soil that could contribute to Factor 1. In the same
direction is Diamond Materials, a large facility that specializes in con­
crete and asphalt recycling and production, and Contractors Materials
LLC, another large facility listed as a hot mix asphalt plant. The
elemental composition of Factor 2, in combination with the location of
the concrete facilities, indicates that Factor 2 likely derives from these
concrete/asphalt dust sources. The diurnal profiles of both factors peak
between 10:00 a.m. and noon Monday through Thursday, with lower
concentrations on Fridays and very low concentrations on the weekend
(Figs. S13–S14). They also both co-vary with PM10. For both factors,
these trends are consistent with trucks or large vehicles driving over soil
in open lots and entraining the soil into the air, or with trucks moving
concrete or concrete components and creating dust during business
hours.
The contribution of soil/dust and concrete to PM10 was assessed
during air quality periods defined as “Good” (PM10 ¼ 0–54 μg/m3),
“Moderate” (PM10 ¼ 55–154 μg/m3), and “Unhealthy for Sensitive
Groups” (PM10 ¼ 155–254 μg/m3) according to the EPA’s Air Quality
Index (AQI) guidelines (Environmental Protec, 2014b); see Table 4).
When the air quality was defined as “Good,” median concrete dust and
soil dust contributions to PM10 were 8% (IQR ¼ 17%; n ¼ 1003) and 7%
(IQR ¼ 7%; n ¼ 1003), respectively. Under “Moderate” conditions,
concrete contributed a larger portion to PM10, with a median value of
33% (IQR ¼ 21%; n ¼ 130), compared to a median contribution from
soil of 12% (IQR ¼ 8%; n ¼ 130). Similarly, during periods when air
O.S. Ryder et al. Atmospheric Environment: X 6 (2020) 100070

Fig. 6. PMF solution Factors 1–3 plotted as conditional probability function maps (Panels A–C), pollution roses (Panels D–F), and diurnal average. The bottom panel
shows the average diurnal variability for each factor.

quality was “Unhealthy for Sensitive Groups”, the median concrete

Table 4 contribution was 58% (IQR ¼ 14%; n ¼ 7) and the median soil contri­
Median contribution of soil dust, concrete dust, and brake wear to PM10 mass
bution was 19% (IQR ¼ 4%; n ¼ 7). Across all AQI categories, concrete
during time periods defined as “Good,” “Moderate,” and “Unhealthy for Sensi­
dust is the highest contributor, and is by far the largest portion of PM10
tive Groups,” based on the AQI index.
under moderate and unhealthy AQI, showing the importance of a local
AQI Air n Concrete Dust Soil Dust Brake/Tire
emission source on the community.
Quality (hours) Wear
Designation In contrast to Factors 1 and 2, Factor 3 presents a markedly different
median IQR median IQR median IQR signature, with comparatively high concentrations of arsenic, lead, zinc,
Good (PM10: 1003 8% 17% 7% 7% 4% 3% copper, barium, and BC. The presence of zinc and copper has been linked
0–54 μg/ to tire wear (Jeong et al., 2019; Hjortenkrans et al., 2007; Councell et al.,
m3)
2004; Harrison et al., 2012; Wahlin et al., 2006; Apeagyei et al., 2011;
Moderate 130 33% 21% 12% 8% 2% 3%
(PM10: Pant and Harrison, 2013). Zinc was identified as the most abundant
55–154 μg/ heavy metal present in tire wear due to the addition of ZnO and ZnS
m3) during tire’s production’s rubber vulcanization process (Adamiec et al.,
Unhealthy 7 58% 14% 19% 4% 0% 1% 2016; Ozaki et al., 2004). Additionally, Adamiec et al. state that over the
(PM10:
155–254
course of a tire’s lifetime, the tire is expected to lose 1.5 kg in weight to
μg/m3) the environment due to road abrasion (Adamiec et al., 2016). Another
source of secondary vehicle emissions is brake linings, which produce
particles when the action of braking induces friction on brake pads and
drums. Contributions from iron, copper, barium, lead, nickel, chromium
and zinc have been reported in differing amounts depending on the

11
O.S. Ryder et al.
brake composition and function of the brakes (Hays et al., 2011; Ada­
miec et al., 2016; Dillner et al., 2005; Lough et al., 2005; Hjortenkrans
et al., 2007; Westerlund, 2001; Blau, 2001; Thorpe and Harrison, 2008;
Environmental Protec, 1998). These signatures all indicate a source
linked to vehicular emissions, which is further supported by the high
contribution of BC in this factor and by the correlation (r2 ¼ 0.65) with
the NOx diurnal profiles (Fig. S15). For these reasons, Factor 3 was
assigned to secondary vehicle emissions.
The pollution plot and CBPF plot for Factor 3 are consistent with the
initial assignment that these particles are predominantly from vehicular
emissions. The pollution rose plot and CBPF maps indicate that this
factor has its highest contribution under lower wind conditions, gener­
ally under 2 m/s, implying a local source near Eden Park. The CBPF plot
also indicates that the highest probability of contributions in the 90th
percentile occurs when winds are minimal or low and from the south­
east, the direction of I-495 (see Fig. 1).
In summary, a 3-factor solution was the best fit to the Eden Park data
and allowed for determination of a local soil/dust factor, a concrete dust
factor, and a brake/tire wear factor. The concrete and soil factors were
differentiated from each other by the high calcium concentration in the
concrete factor —likely deriving from the high concentration of calcium
in limestone and other components used for concrete manufactur­
ing—and by the ratios of elements in the soil factor, resembling the
ratios from two local soil samples. The brake/tire wear factor had strong
contributions from BC and metals including zinc, copper, and lead, all
previously measured as components present in degradation of tires and
vehicle brakes; these contributions are consistent with a relationship to
vehicles.
Table 4 shows the contributions of brake/tire wear to PM10 under
different air quality conditions during the study. It also shows the
contribution of BCBB and BCFF to black carbon during these times.
Compared to concrete dust and soil dust, brake/tire wear contributed
less to PM10 across all air quality conditions. Brake/tire wear’s
maximum contribution was under “Good” conditions, with a median of
4% (IQR ¼ 3%). Under all air quality conditions, the contribution of
fossil fuel to black carbon was greater than the contribution of biomass
burning, with a maximum median value of 87% (IQR ¼ 6%) under
“Moderate” conditions.
5. Conclusion
We used a combination of high-time-resolution instruments to
measure numerous species to understand concentrations and sources of
toxic metals and other pollutants in the EJ community of Eden Park. This
type of customized, focused study can help community members, public
agencies and local stakeholders understand and develop mitigation
strategies for EJ communities that do not have routine air pollution
monitoring. During this study, all species concentrations fell below the
one-in-a-million cancer and non-cancer risk thresholds with the excep­
tion of arsenic, which was slightly above the cancer threshold. Transient
high concentration spikes of arsenic, lead, chromium, and nickel
occurred, but not with sufficient regularity to identify their sources.
Spikes in lead and arsenic did not occur with spikes in soil or biomass
burning indicators, suggesting that arsenic and lead were not from local
soil or burning. With PMF, three factors were identified: soil/dust,
concrete dust, and brake wear/tire emissions from vehicles. On average,
concrete dust contributes 10% (IQR ¼ 20%) and soil contributes 7%
(IQR ¼ 8%) of PM10. As the PM10 concentration increases from the
“Good” to “Unhealthy for Sensitive Groups” AQI category, concrete
emissions account for a greater portion of PM10 compared to soil/dust.
Results from this work are being used by DNREC to work with local
community members and industrial representatives on reducing emis­
sions of concrete dust in the Eden Park community.
12
Atmospheric Environment: X 6 (2020) 100070
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
CRediT authorship contribution statement
Olivia S. Ryder: Formal analysis, Data curation, Writing - original
draft, Writing - review & editing. Jennifer L. DeWinter: Conceptuali­
zation, Methodology, Software, Supervision, Project administration.
Steven G. Brown: Conceptualization, Methodology, Writing - original
draft, Writing - review & editing, Supervision, Project administration.
Keith Hoffman: Conceptualization, Investigation, Supervision. Betsy
Frey: Conceptualization, Investigation, Supervision, Funding acquisi­
tion, Project administration. Ali Mirzakhalili: Conceptualization,
Funding acquisition.
Acknowledgments
The authors would like to thank Dr. Michael McCarthy for helpful
discussions and guidance during data analysis and Levi Stanton for in­
strument setup. This work was funded in part by an EPA Multipurpose
Grant to the State of Delaware (AA06346501) and by State of Delaware
Indirect Funds.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.aeaoa.2020.100070.
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