Environment International 173 (2023) 107866

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Environment International
journal homepage: www.elsevier.com/locate/envint

The oxidative potential of airborne particulate matter in two urban areas of

Chile: More than meets the eye
Carolina Molina a, Carlos A. Manzano a, b, Richard Toro A. a, Manuel A. Leiva G a, *
a
Department of Chemistry, Faculty of Science, Universidad de Chile, Las Palmeras 3425, Ñuñoa, Santiago, Chile
b
School of Public Health, San Diego State University, 5500 Campanile Dr., San Diego, CA 92182, United States

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

Handling Editor: Dr. Xavier Querol Oxidative potential (OP) has gained attention as a parameter that can reveal the ability of different properties of
particulate matter (PM) to generate reactive oxygen species (ROS) as one single value. Moreover, OP is also
Keywords: believed to be a predictor of toxicity and hence the health effects of PM. This study evaluated the OP of PM10,
Oxidative potential PM2.5, and PM1.0 samples using dithiothreitol assays in two cities of Chile (Santiago and Chillán). The results
Particulate matter
showed that the OP was different between cities, PM size fractions, and seasons. Additionally, OP was strongly
Chile
correlated with certain metals and meteorological variables. Higher mass-normalized OP was observed during
Air quality index
Pollution episodes cold periods in Chillán and warm periods in Santiago and was associated with PM2.5 and PM1. On the other hand,
volume-normalized OP was higher during winter in both cities and for PM10. Additionally, we compared the OP
values to the Air Quality Index (AQI) scale and found cases of days that were classified as having “good” air
quality (supposed to be less harmful to health) showing extremely high OP values that were similar to those on
days that were classified as “unhealthy”. Based on these results, we suggest using the OP as a complementary
measure to the PM mass concentration because it includes important new information related to PM properties
and compositions that could help improve current air quality management tools.

1. Introduction (Jorquera et al., 2020, Solís et al., 2022).

Air pollution is widely recognized as a threat to human health,
ecosystems, and even the global economy (Shaddick et al., 2020). One of
the key indicators of air pollution and air quality is the mass concen­
tration of atmospheric particulate matter (PM). Currently, almost 87 %
of the global population is exposed to annual mean concentrations of
PM2.5 (PM with aerodynamic diameter < 2.5 µm) that are above the
guidelines set by the World Health Organization (WHO) (5 μg m− 3), and
over 4 million cases of annual premature deaths have been attributed to
PM exposure (Shaddick et al., 2020; Brauer et al., 2016). In Chile, the
national air quality standards for annual mean concentrations of PM2.5
(20 μg m− 3) and PM10 (50 μg m− 3) are frequently exceeded (Molina
et al., 2017, Li et al., 2022), and approximately 90 % of the population
(15 million people) is estimated to be exposed to PM concentrations that
can affect their health (MMA, 2017). Although prevention and decon­
tamination plans have been implemented to control industrial, vehic­
ular, and wood-burning emissions and the concentrations of PM in
several urban centers have decreased in recent years, national air quality
standards and international guidelines continue to be exceeded
Human exposure to PM and its constituents (e.g., inorganic and
organic compounds) has been associated with adverse health effects
such as respiratory diseases (i.e., asthma), cardiovascular diseases (i.e.,
congestive heart failure, ischemic heart disease), mortality from lung
cancer, neurodevelopment effects in children and cognitive impairment
in the elderly, low birth weight, and an increase in preterm birth (Cohen
et al., 2017; Landrigan et al., 2018; Kilian and Kitazawa, 2018;
Raaschou-Nielsen et al., 2016; Eeftens et al., 2014). Current research
suggests that some components of inhaled PM may induce the genera­
tion of reactive oxygen species (ROS) through oxidation–reduction re­
actions (redox) or biological processes (Valavanidis et al., 2013; Yang
and Omaye, 2009). An imbalance between the generated ROS and the
natural antioxidant defenses of the human body can cause oxidative
stress, which leads to the degradation of macromolecules or cell dete­
rioration and death (Venkatachari et al., 2007). Thus, estimation of the
capacity of PM to generate ROS is relevant to the understanding of the
potential health effects of its exposure and composition (Jomova &
Valko, 2011; Cho et al., 2005; Abrams et al., 2017; Bates et al., 2019).
This capacity has been described as the oxidative potential (OP) of the

* Corresponding author at: Department of Chemistry, Faculty of Science, Universidad de Chile, Las Palmeras 3425, Ñuñoa, Santiago, Chile (M.A. Leiva G.).
E-mail address: manleiva@uchile.cl (M.A. Leiva G).

https://doi.org/10.1016/j.envint.2023.107866
Received 27 November 2022; Received in revised form 2 March 2023; Accepted 3 March 2023
Available online 7 March 2023
0160-4120/© 2023 The Author(s). 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/).
C. Molina et al.
PM (Molina et al., 2020a, 2020b). Different methodologies have been
used to estimate the OP of PM, from epidemiological and in vivo studies
to cellular and acellular assays. The latter has been widely used because
it is low-cost, easy to implement, and positively associated with bio­
logical assays (Molina et al., 2020a, 2020b). Among those assays, some
measure ROS formation over time, while others evaluate the depletion
of a molecule (proxies to cellular reductants) due to the presence of PM
components and ROS (Bates et al., 2019).
The dithiothreitol (DTT) assay is one of the most commonly used
approaches to estimate the OP of environmental samples. It evaluates
the consumption of DTT over time when exposed to components of PM
or other samples (i.e., nanomaterials). It is correlated with diverse
health endpoints (i.e., asthma, congestive heart failure, and ischemic
heart disease) and has shown high sensitivity for organic compounds
and transition metals (Charrier and Anastasio, 2012; Molina et al.,
2020a, 2020b.
The OP of atmospheric PM has been evaluated in several urban
centers and industrial locations worldwide. However, very few of these
studies have reported the OP of samples collected in South America (de
Jesus et al. (2018); Barraza et al., 2020; Andrade et al., 2020). This work
aims to characterize the annual and spatial variability of the OP of three
PM fractions (PM10, PM2.5, and PM1.0) collected at two urban sites in
Chile with different emission sources and where the national air quality
guidelines are often exceeded. Santiago is one of the most populated
cities in South America (approximately 7 million inhabitants), with an
active decontamination plan that seeks to control diverse emission
sources (Barraza et al., 2017). Chillán represents mid-sized cities in
southern Chile, where at least 80 % of PM emissions come from biomass
burning for heating and cooking (MMA, 2017). Adverse health effects
have been observed at both sites. In Chillán, there has been an increase
in emergency room visits for acute respiratory infection and bronchitis
with the increase in PM concentrations (Remaggi et al., 2019: Cifuentes
et al., 2020). In Santiago, a 10 μg m− 3 increase in PM2.5 concentration
increases the risk of hospitalization in children for respiratory diseases
Fig. 1. Geographical location of Chile in the continent and location of Santiago (STG) and Chillán (CHI) in Chile (left panel). Middle panel show location of the
sampling sites in the cities and right panels show a street view around the sampling sites.
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Environment International 173 (2023) 107866
by 2 to 5 % (Matus & Oyarzún, 2019) and the mortality and mobility
related to cardiovascular diseases by 1.3 % (Leiva et al., 2013; Valdés
et al., 2012). The influence of the elemental composition of the PM and
meteorological variables such as air temperature, relative humidity,
wind speed, and direction are also analyzed. Finally, we discuss the
association between the OP and the Air Quality Index developed by the
US EPA and how the inclusion of OP could improve air quality man­
agement tools in a country that has focused its research efforts on the
determination of the mass concentration of PM (Manzano et al., 2020).
2. Methods
2.1. Sampling area
Ambient PM samples were collected at two urban sites: 1) within the
Santiago metropolitan area (site STG: –33◦ 28′ 07′′ , − 70◦ 35′ 45′′ , 570 m
above sea level), on the rooftop of the Faculty of Science of the Uni­
versity of Chile and 2) within the city of Chillán (site CHI: − 36◦ 36′ 23′′ ,
− 72◦ 06′ 16′′ , 130 m above sea level), on the rooftop of the University of
Bío-Bío (Fig. 1).
STG, the capital of Chile, is in a valley in the central zone, and over
7.5 million inhabitants (43 % of the country) live there. The PM sources
in STG are distributed evenly among residential, vehicular, and indus­
trial sources (Barraza et al., 2017; Gallardo et al., 2018; Barraza et al.,
2014, Barraza et al., 2017; Jorquera and Barraza, 2012; Villalobos et al.,
2015). Anticyclonic conditions (a large circulation of winds around an
area of high atmospheric pressure) in the area constantly lead to thermal
inversions (at an altitude of 200 to 400) and atmospheric stability in the
lower troposphere (Toro et al., 2019). Thus, STG has stagnant air that
favors the accumulation of air pollutants (Muñoz and Corral, 2017). The
sampling site in STG was set up in a residential (upper-middle income)
and commercial area with heavy vehicular traffic (>40,000 vehicles per
day) (MTT, 2016) (Fig. 1).
CHI is located in a valley 400 km south of STG. It is a medium-sized
C. Molina et al.
city with 184,739 inhabitants (mostly low and lower-middle income)
(MDS, 2018; INE, 2017). Wood burning is the primary source of PM in
CHI (>80 % of PM emissions) (MMA, 2017). The sampling site in CHI
was located in the downtown area, with a vehicular flow of approxi­
mately 20,000 vehicles per day (SECTRA, 2006). (Fig. 1).
Although both cities have shown relatively high and similar mass
concentrations of PM (the tri-annual mean from 2017 to 2020 was
approximately 30 μg m− 3) (MMA, 2021), CHI commonly shows a larger
number of haze events compared to STG, which can be an effect of the
local meteorological variables and changes in PM emission sources
(Molina et al., 2017).
2.2. PM sampling
Samples containing three PM fractions, PM1.0, PM2.5, and PM10, were
collected between June 2018 and October 2019 (the total number of
samples collected is included in Table S1 in the supplementary material)
using glass fiber filters (1.6 µm pore size, GF/A, Whatman, Maidstone,
UK) and high-volume samplers (model CAV-A/mb, MCV SA, Barcelona,
Spain) with a nominal flow rate of 30 m3/h for 24 h (midnight to
midnight). All filters were conditioned for 24 h before sampling in a
controlled environment at a relative humidity of 20 ± 2 % and a tem­
perature of 20 ± 2 ◦ C and then weighed using a high-precision micro­
balance (0.01 mg, Radwag XA 110/4Y, Radwag, Torunska, Poland)
equipped with an antistatic source of Polonium-210 (Model DJ-02,
Radwag, Torunska, Poland). After sampling, the filters were reweigh­
ted and stored in sealed containers at − 20 ◦ C until analysis.
2.3. Oxidative potential
The OP of the collected PM samples was quantified using the DTT
assay (Charrier and Anastasio, 2012; Cho et al., 2005; Li et al., 2009; Lin
and Yu, 2019). A detailed description of this method, including an
analysis of its uncertainty, can be found in previous research (Molina
et al., 2020a, 2020b). Briefly, subsections of the filters were extracted by
sonication in ultrapure deionized water (18 Ohm). The extracts were
filtered using 0.45 μm PTFE syringe filters. A 3.5 mL aliquot of each
extract and 1.0 mL of potassium phosphate buffer (pH 7.4, pretreated
with Chelex ® to remove trace metals) were mixed in a vial. Then, 0.5
mL of a DTT stock solution (1 mM) was added to the reaction mix with
constant shaking. Aliquots of 0.5 mL were extracted from the reaction
mix every 5 or 10 min (i.e., at 0, 5, 10, 20 and 30 min) and were added to
1 mL of 5,5′ -dithiobis (2-nitrobenzoic acid) (DTNB) solution (1 mM).
The product, 2-nitro-5-thiobenzoic acid (TNB), was quantified using
UV–visible spectrophotometry at 412 nm. All reaction vials were pro­
tected from direct light while sample analysis was performed. Labora­
tory blanks, field blanks, and 9,10-phenanthrenequinone (positive
control) were used for QA/QC protocols (130 blank replicates and 80
positive controls showed a relative standard deviation below 15 %).
Each sample was analyzed in triplicate, and a previously estimated
expanded uncertainty (U = 16 %) was applied to validate the results (a
parameter that characterizes the dispersion of values measured with 95
% confidence) (Molina et al., 2020a, 2020b).
The OP results were normalized by the total mass of the collected PM
(DTTm, in pmol of DTT consumed min− 1 μg− 1 of PM) and by the total
volume of sampled air (DTTv, in nmol of DTT consumed min− 1 m− 3 of
air). OP mass normalization is a useful metric that describes the intrinsic
ability of the PM to oxidize a target molecule or produce redox species.
On the other hand, the volume-normalized OP describes this ability
considering the concentration of PM measured in a unit of air volume,
which represents an air quality measure.
2.4. Elemental analysis
The water-soluble concentrations of elements in the collected PM
were measured using total reflection X-ray fluorescence spectroscopy
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Environment International 173 (2023) 107866
(TXRF, S2 PICOFOX, Bruker, Billerica, MA, USA). A detailed description
of this method can be found in previous research (Towett et al., 2013).
Briefly, PM extracts were combined with a standard solution of Ga.
Then, 10 µL of the mix was placed on a quartz cell for measurement
(detection limits between 5 × 10-4 to 1.5 mg/L, Table S2). A total of 88
(CHI, PM1.0: 10; PM2.5: 23 and PM10: 23; STG, PM2.5: 16 and PM10: 16)
samples were analyzed. The elements analyzed were sulfur (S), chlorine
(Cl), potassium (K), calcium (Ca), titanium (Ti), manganese (Mn), iron
(Fe), nickel (Ni), copper (Cu), arsenic (As), selenium (Se), bromine (Br),
strontium (Sr), barium (Ba), and lead (Pb).
2.5. Statistical analysis
Statistical analysis was performed using Microsoft Excel (Microsoft
Corporation, Redmond, WA, USA) and R programming language using
the OpenAir package (Carslaw and Ropkins, 2012). Sampling sites, PM
fractions, and sampling periods were compared using the Kruskal-Wallis
test (nonparametric method for comparing k independent samples),
while Spearman’s correlations (nonparametric measure of rank corre­
lation) were used to evaluate the relationship between the OP, the
chemical components (metals), and the meteorological variables
measured at both sites using a Vantage Pro monitoring station (Davis
Instruments, USA). Seasonality was considered to evaluate the results, in
which the cold period was defined as occurring between April and
September, while the warm period was defined as occurring between
October and March.
3. Results and discussion
3.1. PM mass concentration
A total of 527 PM samples were collected (STG: 247 samples and
CHI: 280 samples). The annual mean concentrations (and range)
measured for the collected PM10, PM2.5 and PM1.0 samples were 59.2 ±
30 (7.7–55.2), 28.6 ± 18 (6.3–87.9) and 19.3 ± 11 (3.6–53.4) μg m− 3,
respectively, in STG and 35.7 ± 30 (9.1–131.1), 26.0 ± 27 (6.0–127.1),
and 31.2 ± 26 (5.6–114.1) μg m− 3, respectively, in the CHI (Fig. 2,
Table 1, Figure S1 and Table S3). Seasonal variability was observed for
the PM10 and PM2.5 concentrations at both sampling sites, with lower
concentrations during warmer months (September to February) and
higher concentrations during colder months (March to August) (Kruskal-
Wallis, p < 0.05). The PM2.5/PM10 ratios were higher during colder
months (between 0.7 and 0.8) than during warmer months (between 0.2
and 0.6) (Kruskal-Wallis, p < 0.05). These observed differences can be
explained in part by the increase in anthropogenic emissions from res­
idential heating systems (i.e., biomass burning) and unfavorable
dispersion conditions during colder months in both cities (Morales-Solís
et al., 2021). Similar values were observed for annual mean mass con­
centrations of PM2.5 (STG: 18 to 30 μg m− 3; CHI: 17 to 40 μg m− 3) and
PM10 (STG: 50 to 70 μg m− 3; CHI: 35 to 50 μg m− 3) in previous studies
(Jorquera et al., 2020; MMA, 2021; Morales-Solís et al., 2021).
3.2. Oxidative potential
The monthly means of the OP (DTTv and DTTm) of the PM10, PM2.5,
and PM1.0 samples collected at both sites are shown in Fig. 2.
DTTm: The mean DTTm values for PM10, PM2.5, and PM1.0 in STG
were 9.43 (range: 5.6–15.6), 14.4 (range: 6.8–27.8), and 13.50 (range:
9.7–19.0) pmol min− 1 μg− 1, respectively (Fig. 2). The mean DTTm
values in CHI were 15.7 (range: 14.6–16.9), 20.2 (range: 4.1–32.2), and
25.7 (range: 13.4–39.8) pmol min− 1 μg− 1 for PM10, PM2.5, and PM1.0,
respectively (Fig. 2). PM2.5 and PM1.0 showed higher DTTm values than
did PM10. This was expected since the DTT assay has shown a higher
sensitivity for smaller particles, related to their larger surface area or
emission sources and the fact that small particles dominate the available
surface area and the total number of particles compared to other size
C. Molina et al. Environment International 173 (2023) 107866

Fig. 2. Monthly distribution for PM mass concentration, DTTm and DTTv of PM1.0 (blue), PM2.5 (green) and PM10 (red) for sites STG and CHI.

Table 1
Seasonal averages and standard deviations of concentration, DTTm and DTTv for PM1.0, PM2.5 and PM10 in STG and CHI.
Site Season Concentration DTTm DTTv
(µg/m− 3(− |-)) (pmol DTT min− 1
µg− 1) (pmol DTT min− 1
m− 3)

PM1.0 PM2.5 PM10 PM1.0 PM2.5 PM10 PM1.0 PM2.5 PM10

STG Autumn 24 ± 7 37 ± 14 76 ± 25 14 ± 3 12 ±3 8±2 319 ± 88 425 ± 98 610 ± 124

Spring 16 ± 7 43 ± 14 17 ±3 10 ± 2 271 ± 104 406 ± 129
Summer 14 ± 4 39 ± 14 17 ±6 10 ± 1 232 ± 91 377 ± 117
Winter 41 ± 19 75 ± 33 13 ±4 10 ± 3 508 ± 175 675 ± 225
CHI Autumn 43 ± 32 42 ± 35 58 ± 41 23 ± 5 21 ±4 15 ± 3 909 ± 503 753 ± 513 786 ± 515
Spring 10 ± 4 9±4 22 ± 10 23 ± 6 18 ±7 12 ± 5 213 ± 77 160 ± 91 238 ± 110
Winter 29 ± 22 31 ± 23 43 ± 29 28 ± 9 22 ±5 19 ± 6 731 ± 471 714 ± 489 799 ± 559

fractions (secondary formation or burning process) (Khoshnamvand
et al., 2022; Molina et al., 2020a, 2020b). The mean DTTm for PM2.5 was
1.5 and 1.4 times higher than that for PM10 (in STG and CHI, respec­
tively, Kruskal-Wallis, p < 0.05). Similarly, the mean DTTm for PM1.0
was 1.4 times higher than that for PM2.5 in CHI (Kruskal-Wallis, p <
0.05), but it was not significantly different in STG (Kruskal-Wallis, p >
0.05).
The difference between STG and CHI in terms of DTTm values was
enhanced during colder months (May-August), in which the value at CHI
almost doubled what was observed at STG (Kruskal-Wallis, p < 0.05).
This was more evident in smaller PM fractions (Fig. 2). This difference
was attributed to the seasonality observed in CHI, where the DTTm
showed the highest values in colder months for all PM fractions, while
the lowest values (approximately-one-half) were observed in summer
(Kruskal-Wallis, p < 0.05) (Fig. 2). However, this was not observed in
STG, where PM10 did not show seasonal variability and PM2.5 showed
local maximum values in warmer months (November-January) and
minimum values during colder months (Kruskal-Wallis, p < 0.05).

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C. Molina et al.
The differences observed between sampling sites could be related to
the different local PM emission sources at each site. The major emission
sources of PM in STG are vehicular, industrial (which are consistent
year-round), and wood burning emissions (Barraza et al., 2017; Villa­
lobos et al., 2015). Wood burning for residential heating is banned in
STG; however, it is still used illegally in colder months. In STG, the
higher DTTm values observed during summer could be associated with
increased photochemical activity in the atmosphere. Previous studies
have shown that oxidized compounds have higher redox activity than
their precursors (Jiang et al., 2020). It has been shown that the fraction
of low-volatility oxygenated organic aerosols can double from August to
November in STG (Carbone et al., 2013). These highly oxidized species
contribute to the OP of the collected PM (Paraskevopoulou et al., 2019;
Verma et al., 2015) in warmer months, reducing the seasonality of the
DTTm values in STG.
DTTv: The mean DTTv values were higher in STG, with values of
0.53 (range 0.15–1.52), 0.38 (range 0.07–0.979), and 0.32 (range
0.19–0.47) nmol min− 1 m− 3 for PM10, PM2.5 and PM1.0, respectively
(Kruskal-Wallis, p < 0.05). This was expected since DTTv is directly
connected to the atmospheric mass concentration of PM. However, no
significant differences were observed in the DTTv among PM sizes in
CHI, with values of 0.56 (range 0.09–2.78), 0.66 (range 0.03–1.94), and
0.71 (range 0.13–1.74) nmol min− 1 m− 3 for PM10, PM2.5 and PM1.0,
respectively (Kruskal-Wallis, p > 0.05) (Fig. 2). These results demon­
strate that the intrinsic OP for PM2.5 and PM1.0 particles at CHI are
higher even when their ambient mass concentration is lower than that of
PM10 particles. Although the highest DTTv was observed during winter
months for both sampling sites, the intensities of the observed maxima
were different, being 2 to 3 times higher in STG and 3 to 4 times higher
in CHI compared to the summer values (Fig. 2). Similarly, some winter
DTTv values in CHI were 3 times higher than those measured in STG
Fig. 3. Comparison for DTTm, DTTv among world cities. * box limits are standard deviation instead of range (minimum and maximum).
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Environment International 173 (2023) 107866
(Kruskal-Wallis, p < 0.05). However, the DTTv in STG was significantly
higher during summer (Kruskal-Wallis, p < 0.05) compared to that in
CHI, possibly related to an increase in photochemical activity in the city
(Menares et al., 2018). This indicated differences and changes in the
emission sources in each season. Thus, the high seasonal variability of
the DTTm and DTTv in CHI suggested a potential connection with local
winter emissions, mainly wood burning used for residential heating,
which contributes over 80 % of the total PM emissions (Álamos et al.,
2021). Additionally, the low quality of the wood used (i.e., high mois­
ture content) generates an inefficient combustion process, which implies
higher emissions of chemicals that can contribute to an increased OP of
local PM (i.e., NOx, black carbon, phenols, polycyclic aromatic hydro­
carbons, among others) (Gramsch et al., 2016; Guerrero et al., 2019:
Park et al., 2018). Other cities in southern Chile, such as Temuco and
Coyhaique (in which wood burning is the primary PM emission source),
have shown higher concentrations of PAHs in winter (Bravo-Linares
et al., 2012; Scipioni et al., 2012; Villalobos et al., 2017). Additionally,
the poor thermal insulation of homes in CHI and the relatively low cost
of firewood can increase firewood consumption and thus the DTTv at
this site (Urquiza et al., 2019). The reduction in wood-burning emissions
at CHI in summer led to a decrease in the OP and PM mass concentra­
tions, which explained the differences with STG, where other PM
emission sources coexisted and remained constant throughout the year.
This explanation also applied in winter, when those emissions increased,
and even if the mass concentrations in STG were higher, the oxidative
capacity of the PM at CHI was considerably higher.
Differences among sites: The mean DTTm of the PM10 in STG was
similar to what has been reported in Salento (Pietrogrande et al., 2018a,
2018b) and Lecce (Chirizzi et al., 2017) (between 0.08 and 0.011 nmol
min− 1 μg− 1), which are both in Italy, while the DTTm of the PM2.5
(0.015 ± 0.004 nmol min− 1 μg− 1) showed similar values to those of
C. Molina et al. Environment International 173 (2023) 107866

Lecce (Chirizzi et al., 2017) and the U.S. Midwest (0.014 range:
0.004–0.032 nmol min− 1 μg− 1) (Yu et al., 2021) (Fig. 3). The DTTm for
PM10 in CHI was similar to that in Mount Abu (0.015 ± 0.009 nmol
min− 1 μg− 1) (Patel & Rastogi, 2018), while the DTTm of PM2.5 in CHI
(mean: 0.02 ± 0.01 nmol min− 1 μg− 1) was comparable to that in Atlanta
(0.024 ± 0.008 nmol min− 1 μg− 1) (Gao et al., 2020a, 2020b, 2020c).
Similar results were observed for the DTTv, with the previously
mentioned sites showing comparable results to the PM10 and PM2.5 at
both sites (Fig. 3). PM2.5 in CHI showed similar values to those in
Hangzhou, which also has vehicle, coal, and wood burning emissions
(Wang et al., 2020). The DTTv values of PM1.0 are reported in the
literature for only two cities, Brno (0.007, range: 0.003 to 0.012 nmol
min− 1 m− 3) (Cigánková et al., 2021) and Lin’an, Hangzhou (0.79 ±
0.25 nmol min− 1 m− 3) (Li et al., 2021), and these values are in the range
of those reported for STG (0.32 ± 0.09 nmol min− 1 m− 3) and CHI (0.72
± 0.50 nmol min− 1 m− 3).
Elemental composition and oxidative potential: The measured
concentrations of the selected elements in the samples collected during
cold and warm periods at both sites are shown in Tables S4 and S5. In
general, higher concentrations of S, Se, and Cu (except for the PM2.5
fraction during summer) were found in STG. In addition, higher K, Br,
and Pb concentrations were found in CHI during the cold season (mass
and volume normalized). Cu and Fe (elements with higher redox ac­
tivity) (Charrier and Anastasio, 2012) were found in higher concentra­
tions during cold months in STG than in CHI. However, Cu
concentrations were higher at both sites in summer, which might
explain the relatively high OP observed for the samples collected in STG
during this period (Gao et al., 2020a, 2020b, 2020c; Zhao et al., 2015).
Additionally, PM2.5 showed the largest concentration of K at both sites.
No significant correlations were observed between the DTTm and the
concentrations of the elements found in the samples (Table S6). How­
ever, Zn, K, and As showed a significant correlation (Spearman) with
DTTm in CHI, demonstrating the effects of wood or coal burning in the
area through the tracers for those emission sources (Jorquera et al.,
2018; Blanco-Alegre et al., 2022). The positive correlation between
DTTm and certain nonredox active elements can be explained by the Fig. 4. (a) Air temperature; and (b) Polar Plot for DTTm and DTTv at both sites.
simultaneous emission (from the same source) of active compounds that
increase the OP (Gao et al., 2020a, 2020b, 2020c). known emission sources in STG during the summer (which would favor
The S, K., Fe, Br, As, Zn, Ca, Mn, Ba, and Cu concentrations showed the formation of photochemical products) that could increase the
positive and significant Spearman’s correlations with the DTTv at both oxidative capacity of PM.
sites, which has been reported in other studies (Cheung et al., 2010; This result could have been connected to the formation process of
Boogaard et al., 2012, Fang et al., 2017; Malakootian et al. 2022). This secondary organic aerosols (SOAs), which is favored by high tempera­
could be connected to vehicles being the primary source of emissions, oil tures and low relative humidity, increasing the volatilization of organic
combustion, or secondary particles (Prieto-Parra et al., 2017; Rubio components that can be oxidized by hydroxyl radicals, nitrogen oxides
et al., 2018; Watson & Chow, 2014; Richter et al., 2007). and ozone (which were previously reported in high concentrations in
Meteorological variables: The mean, standard deviation, and range STG) (Seguel et al., 2020; Gramsch et al., 2020), thus increasing the OP
for the meteorological variables of CHI can be found in Table S7 for STG of PM oxidative potential (Emanuelsson et al., 2013; Rossignol et al.,
and Table S8. The PM mass concentration for all fractions generally 2016). Additionally, solar radiation regulates the concentrations of NOx
showed negative Spearman’s correlations (p < 0.05) with air tempera­ and ‧OH, as well as biogenic and anthropogenic emissions of volatile
ture, wind speed, and precipitation at both sites (Table S9). These results organic compounds (VOCs) (Tuet et al., 2017). With the increase in air
showed the effect of higher wind speeds on dispersion and thus lower temperature, the emission of VOCs also increases, which could also in­
concentrations of pollutants in the atmosphere at both sites, especially in crease the OP of PM in STG in warm months.
winter, when wet deposition can further reduce their concentrations. The DTTv value in STG and CHI showed the expected distributions
However, this correlation does not imply causation, since this could also and correlations with air temperature since it is directly affected by PM
be related to changes in PM emission sources. concentrations. DTTv reached its maximum value during colder months
The relationship between DTTm, DTTv, and temperature is shown in and its minimum value in warmer months at both sites (Fig. 4a). The
Fig. 4a for PM10 and PM2.5. A DTTm maximum for PM2.5 occurred relationship between temperature, wind speed, and Rs in the summer
during high air temperatures in STG but not in CHI, which reinforced the samples can be determined by principal component analysis (Figure S2).
positive correlation observed between DTTm and air temperature dur­ Additionally, the winter samples at both sites were related to OP and K.
ing spring. PM1.0 was expected to show similar results to those of PM1.0 The variables were distributed over the same area as the samples for
in STG in the spring and summer months, but the number of samples was each season. The winter samples were distributed over the left side, and
insufficient to substantiate this expectation. Different results were the summer samples were over the right side for both sites. Comparing
observed for PM10 and DTTm in STG. In CHI, the DTTm maximum for the sample distribution by site, the CHI sample group was located in the
both PM2.5 and PM10 was measured during the cold season. Although lower section of the figure, while STG samples were in the upper section.
these results reinforced the fact that the impact of wood-burning emis­ Polar plots showed the wind direction from where the higher DTTm
sion sources was very important during winter in CHI, there were fewer

6
C. Molina et al.
and DTTv values occurred (Fig. 4b and Figure S3). Higher DTTv values
were found during calm conditions (lowest wind speeds), indicating that
local emission sources were important contributors. However, higher
DTTm values were found to be correlated with southwest winds in STG
and northern winds in CHI, where an industrial area is located (agri­
culture and livestock farming). Thus, bioaerosols, secondary particles
with high contents of ammonia, sulfate, nitrates, and VOCs, were pro­
duced by those sources (Kundu and Stone, 2014).
OP and air quality index (AQI): The United States Environmental
Protection Agency (US EPA) defines the ranges of PM concentrations
that can represent a risk to human health in an air quality index (AQI)
(Al-Saadi et al., 2005). The AQI uses a normalized scale from 0 to 500
and is divided into six categories according to health concerns and
recommendations (For PM1.0 and PM2.5: Good (G) < 12 μg m− 3, Mod­
erate 12–35.5 μg m− 3, Unhealthy for sensitive groups (US) 35.5–55.5 μg
m− 3, Unhealthy (U) 55.5–150.5 μg m− 3, Very unhealthy (VU)
150.5–250.5 μg m− 3, and Hazardous (H) > 250.5 μg m− 3; For PM10:
Good < 55 μg m− 3, Moderate 55–155 μg m− 3, Unhealthy for sensitive
groups 155–255 μg m− 3, Unhealthy 255–355 μg m− 3, Very unhealthy
355–425 μg m− 3, and Hazardous > 425 μg m− 3) (Sarmadi et al., 2021).
The measured PM concentrations, classified according to the AQI
index, were compared with the DTTm and DTTv values. Very unhealthy
and hazardous conditions, according to the AQI, were not observed. As
expected, DTTv was positively correlated with the AQI (Figs. 5 and 6),
particularly in CHI. The DTTv values were significantly higher during
conditions that were unhealthy and unhealthy for sensitive groups, ac­
cording to the AQI(Kruskal-Wallis, p < 0.05), which occurred on days
with a higher PM mass concentration related to wood-burning emis­
sions. Additionally, the DTTv in CHI nearly doubled that measured in
STG during unhealthy conditions, which may indicate that, although
these episodes are currently considered to be similar (in terms of their
Fig. 5. Comparison among AQI (good (G), moderate (M), unhealthy for sensitive groups (US), and unhealthy (U)) for PM1.0, PM2.5 and PM10 at both sites.
7
Environment International 173 (2023) 107866
AQI scale), the oxidative capacity of the PM collected in CHI was much
greater than that in STG.
There were also some cases in which a high DTTv had a good or
moderate AQI classification, which demonstrates that solely using the
concentration of PM for environmental management proposes may not
adequately reflect the potential health impacts of some pollution
episodes.
The DTTm was not correlated with the AQI index, and no significant
differences among AQI categories were observed (Kruskal-Wallis, p >
0.05) at CHI (Fig. 5). The DTTm of PM2.5 for good AQI conditions in STG
was significantly higher than that of the other classifications (Kruskal-
Wallis, p < 0.05). This could have been related to the sites having the
same PM sources throughout the sampling period, which may have
produced similar PM compositions regardless of their concentrations in
the atmosphere. This result shows that the oxidative potential, as DTTm,
does not depend on concentration.
Since the threshold above which the OP may reflect adverse health
effects has not yet been clearly defined, it is difficult to compare expo­
sure conditions based on these estimated values (DTTm and DTTv).
However, the DTTm and DTTv in this study showed higher values than
those in other studies, which could be related to the higher incidence of
diabetes, asthma, ischemic heart disease, and the increase in the number
of emergency room visits due to respiratory disease (Strak et al., 2017;
Abrams et al., 2017).
Therefore, incorporating estimations of OP into existing indices such
as the AQI could improve our efforts to protect human health in urban
and rural environments due to the correlation shown between OP esti­
mations and PM composition.
C. Molina et al. Environment International 173 (2023) 107866

Fig. 6. Scatter plot, DTTv and AQI (PM1.0 and PM2.5: Good < 12 μg m− 3, Moderate 12–35.5 μg m− 3, Unhealthy for the sensitive groups 35.5–55.5 μg m− 3, Unhealthy
55.5–150.5 μg m− 3, Very unhealthy 150.5–250.5 μg m− 3; PM10: Good < 55 μg m− 3, Moderate 55–155 μg m− 3, Unhealthy for sensitive groups 155–255 μg m− 3,
Unhealthy 255–355 μg m− 3, Very unhealthy 355–425 μg m− 3) for PM1.0, PM2.5 and PM10 at both sites.

4. Conclusions meteorological variables. Thus, higher DTTv values were measured in

We present the first full-year study of aerosol OP in two Chilean cities
for three different PM fractions, PM10, PM2.5, and PM1.0 (which has been
previously studied in only a few studies), and its relation to the chemical
properties of PM and meteorological variables.
The spatial–temporal variability of OP can be explained by the
emissions at the study sites and the meteorological variables. In CHI,
emissions from wood burning during cold months explains the vari­
ability in the DTTm and DTTv values. In STG, where wood burning is
banned, the increase in PM concentrations is dominated by
winter, controlled by the reduced dispersion of pollutants. DTTm was
higher in summer when the concentration of ozone and radiation
increased at the sites. Those changes were also observed in the PM
fractions, with PM1.0 and PM2.5 showing higher DTTm values than did
PM10 and no differences in DTTv in CHI even when larger particles were
at higher mass concentrations.
Although the AQI has been an effective tool to protect human health,
it should be complemented with OP measurements to establish infor­
mation on the toxicity of PM. Using PM mass concentrations alone may
lead to a misrepresentation of the potential effect on human health and

8
C. Molina et al.
result in poor air pollution management. This work will help to increase
the knowledge of the OP of atmospheric PM in urban cities in developing
regions with air quality problems related to different emission sources.
We also focused on improving the existing environmental management
tools by including the OP of PM as one of the metrics used to evaluate
pollution episodes. However, more detailed research on the relationship
between these tools (technological improvements, economic measures,
environmental education, among others) and the estimated OP is
needed, especially for PM1, which has not been widely analyzed and
might have a higher risk of exposure.
Research data
The raw data are available upon request.
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.
Data availability
Data will be made available on request.
Acknowledgments
This research was funded by the National Agency of Investigation
and Development, Government of Chile (ANID), (ANID/FONDECYT
Grant No. 1200674, grant No. 1118051 and ANID/FONDEQUIP Grant
No. EQM190045). RTA acknowledges the financial support from the
University of Chile (Grant ENLACE-VID 2020 ENL17/20). CM was
supported by Programa Nacional de Becas de Postgrado 2018 (No.
21181015). The authors acknowledge Dr. Hernán Ahumada from the
Department of Natural Sciences, Faculty of Science, Universidad del Bío-
Bío, for providing field support with sampling particulate matter in the
city of Chillan.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.envint.2023.107866.
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