International Journal of

Environmental Research
and Public Health

Article
Chemical Composition and Source Apportionment of
Wintertime Airborne PM2.5 in Changchun, Northeastern China
Shichun Zhang 1, *, Daniel Q. Tong 2 , Mo Dan 3 , Xiaobing Pang 4 , Weiwei Chen 1 , Xuelei Zhang 1 ,
Hongmei Zhao 1 , Yiyong Wang 5 and Bingnan Shang 6

1 Key Laboratory of Wetland Ecology and Environment, Northeast Institute of Geography and Agroecology,
Chinese Academy of Sciences, 4888 Shengbei Street, Changchun 130102, China; [email protected] (W.C.);
[email protected] (X.Z.); [email protected] (H.Z.)
2 Center for Spatial Information Science and Systems, George Mason University, Fairfax, VA 22030, USA;
[email protected]
3 Beijing Municipal Institute of Labor Protection, Beijing 100054, China; [email protected]
4 Institute of Environment, Zhejiang University of Technology, Hangzhou 310006, China;
[email protected]
5 School of Geography and Environment, Baoji University of Arts and Sciences, Baoji 721013, China;
[email protected]
6 Department of Library, Jilin University of Finance and Economics, Changchun 130117, China;
[email protected]
* Correspondence: [email protected]



Abstract: This study presents field observations and laboratory analyses of wintertime airborne


particulate matter (PM2.5 ) and its chemical components in the Changchun metropolitan area, the
Citation: Zhang, S.; Tong, D.Q.; Dan,
geographical center of northeastern China. Twenty-four hour PM2.5 filter samples were collected
M.; Pang, X.; Chen, W.; Zhang, X.;
from 23 December 2011 to 31 January 2012 at four sites in the types of traffic, residential, campus, and
Zhao, H.; Wang, Y.; Shang, B.
a near-city rural village, respectively. Daily PM2.5 concentrations ranged from 49 to 466 µg m−3 , with
Chemical Composition and Source
Apportionment of Wintertime
an arithmetic average of 143 µg m−3 . Laboratory analyses showed that among all measured chemical
Airborne PM2.5 in Changchun, species, mineral dust contributed the largest proportion (20.7%) to the total PM2.5 mass, followed by
Northeastern China. Int. J. Environ. secondary inorganic aerosols (SIA, including SO4 2− , NO3 − and NH4 + ), which constituted 18.8% of
Res. Public Health 2021, 18, 4354. PM2.5 mass. Another notable feature of PM2.5 chemical composition was high halogen (Cl− and F− )
https://doi.org/10.3390/ loadings at all sites, which was likely due to emissions from coal combustion, plastic manufacturing,
ijerph18084354 and glass melting. Among the four sampling sites, the suburban site exhibited the highest PM2.5
levels and extremely high Cl− and F− loadings due to residential wood burning and nearby industrial
Academic Editor: Kihong Park facilities lacking effective emission controls. Our results report one of the earliest observations of
PM2.5 composition in this region, providing a baseline of aerosol profiles of aerosol before PM2.5
Received: 5 March 2021
was routinely measured by environmental protection agencies in China, which could be useful for
Accepted: 14 April 2021
assessing long-term trends of air quality and effectiveness of mitigation measures.
Published: 20 April 2021

Keywords: aerosol; PM2.5 ; measurement; Northeast China; source apportionment

Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
published maps and institutional affil-
iations.
1. Introduction
Exposure to outdoor air pollution causes 4.2 million premature deaths worldwide
every year, making air pollution the single largest environmental risk today [1]. Among
Copyright: © 2021 by the authors.
all pollutants, ozone (O3 ) and PM2.5 (particulate matter with diameter <2.5 µm−3 ) are
Licensee MDPI, Basel, Switzerland.
most closely associated with increased occurrence of lung cancer and cardiovascular
This article is an open access article diseases [2,3]. A large portion of the global health burden is associated with certain Asian
distributed under the terms and countries, where high population densities correlate with elevated air pollution levels [4].
conditions of the Creative Commons Elevated levels of PM2.5 , resulting from rapid economic growth and urbanization in past
Attribution (CC BY) license (https:// decades [5], are common in many regions of China [6–10], posing an unprecedented threat
creativecommons.org/licenses/by/ to regional air quality and human health [11,12].
4.0/).

Int. J. Environ. Res. Public Health 2021, 18, 4354. https://doi.org/10.3390/ijerph18084354 https://www.mdpi.com/journal/ijerph
Int. J. Environ. Res. Public Health 2021, 18, 4354 2 of 18

In the past decades, a number of studies have addressed various aspects of particulate
matter pollution in China, such as spatiotemporal variations [8,13], formation and evolution
mechanisms [14–16], source apportionment [17,18], health effect assessments [12,19], and
mitigation measures and policies [11,20]. Several nationwide studies have presented
national maps of PM2.5 and key components measured at regional background locations
or during field campaigns in major cities [8,10,21]. However, at the time this study was
conducted, similar studies focused mostly on a few economically developed regions in
China, including the Beijing–Tianjin–Tanggu area, the Yangtze River Delta, and the Pearl
River Delta. Knowledge on characteristics and sources of PM2.5 pollution in other regions
(e.g., northeastern China) are still limited, making it difficult to design effective emission
control policies at local, regional, and even national levels.
This study presents detailed observations and analyses of PM2.5 and its chemical
components during wintertime in Changchun, a metropolitan area located in the center
of China’s breadbasket region. Wintertime air pollution in Changchun is shaped by
several environmental settings unique to this region, including low temperatures, a shallow
boundary layer, dense industrial emission sources, coal-dominant energy consumption,
domestic heating with mixed fuel types (i.e., coal, wood), and frequent use of deicing
salts [22]. Changchun is located in the middle of the Chinese “black soil” zone, one of the
world’s three most fertile croplands. Temperatures in Changchun can be as low as −30 ◦ C
in winter, resulting in a planetary boundary layer so shallow that a virtual cap is formed.
This phenomenon prevents dispersion of PM2.5 emitted from an increasing vehicle fleet
and many industrial sources. Unlike heating in Beijing, domestic heating in Changchun
is provided by both large and small coal- and wood-burning boilers, the emissions from
which are more difficult to control than centralized heating systems. Changchun was one
of the largest industrial hubs in China in the 1950s and 1960s, and many facilities are still
operating with updated technology. For example, the car-making industry produces more
than 2 million vehicles per year in this city. It is of interest to investigate how wintertime air
pollution in Changchun is controlled by these environmental settings. To date, a number of
similar studies conducted in northeastern China [23–28] have shown that PM pollution is
very severe during winter. However, very limited studies on PM2.5 mass concentration [29]
and its detailed chemical composition [8,30,31] in Changchun have been conducted so far.
In this paper, we present the detailed observations, taken during an intensive field
campaign, of wintertime PM2.5 and its major components at four sites representing traffic,
residential, campus and suburban village, respectively, in the Changchun metropolitan area.
The objectives of the present study are three-fold: (1) to determine the spatial variability
of PM2.5 levels in Changchun; (2) to investigate the chemical characteristics of PM2.5 ; and
(3) to probe the main sources of PM2.5 during the study period. This study will provide
useful information regarding PM2.5 pollution and its contributing sources in this relatively
under-studied area. This information can be used to inform future decision making on
mitigating particulate matter pollutions. The PM2.5 composition observations presented
here are also expected to improve emission inventories of PM2.5 and provide reliable
constraints for chemical transport models to predict PM2.5 pollution in Northeast China.

2. Materials and Methods

2.1. Description of the Sampling Sites
Changchun (124◦ 180 E–127◦ 020 E, 43◦ 050 N–45◦ 150 N) is located in the center of the
Northeast Plain in China. The Changchun metropolitan area is comprised of 119 townships
in 10 counties, with a total land area of 20,660 km2 and a population of 7.6 million, of which
3.6 million lived in urban areas in 2011 [22]. It is within the North Temperate Zone, which
is characterized by a continental monsoon climate with cold, dry winters and warm, humid
summers. The annual average temperature is 5.2 ◦ C, and the average annual rainfall is
560 mm. The prevailing wind direction is southwest throughout the year, with a mean
wind speed of 4.3 m/s. Temperature inversion, a meteorological condition conducive to
Int. J. Environ. Res. Public Health 2021, 18, x FOR PEER REVIEW 3 of 20

a mean wind speed of 4.3 m/s. Temperature inversion, a meteorological condition condu-
Int. J. Environ. Res. Public Health 2021, 18, 4354 3 of 18
cive to degrading air quality when combined with intense local emissions, occurs fre-
quently in winter [32].
In China,
degrading air coal combustion
quality has beenwith
when combined identified
intense aslocal
one of the largest
emissions, contributors
occurs frequentlyto airin
pollution
winter [32]. [33]. In Changchun in 2011, a total of 25.8 million tons of raw coal were con-
sumed, In among
China, coal which 13.8 million
combustion hastons
beenwere consumed
identified as onebyofthermal power
the largest generationtoand
contributors air
another
pollution [33]. In Changchun in 2011, a total of 25.8 million tons of raw coal were The
4.8 million tons were consumed by wintertime domestic heating [22]. major
consumed,
industries
among which in Changchun
13.8 millioninclude
tons werethe consumed
automotive byindustry, coal-fired
thermal power power plants,
generation met-
and another
allurgy,
4.8 millionirontons
andweresteelconsumed
mills, machine manufacturing,
by wintertime domestic and electric
heating and
[22]. Theelectronics manu-
major industries
facturing,
in Changchun and most includeof these industries industry,
the automotive are located in the western
coal-fired and northern
power plants, portions
metallurgy, iron
of
andChangchun
steel mills,[34].machine manufacturing, and electric and electronics manufacturing, and
mostAoffield
thesecampaign
industrieswas are carried
located out from
in the 23 December
western and northern2011 portions
to 31 January 2012. Ambi-
of Changchun [34].
ent airAwas sampled at four sites in Changchun (Figure 1).
field campaign was carried out from 23 December 2011 to 31 January 2012.These sites included theAmbient
follow-
ing locations:
air was sampled (1) the Chinese
at four sites Academy
in Changchun of Sciences
(FigureInstitute
1). Theseofsites
Geography
includedand theAgroecol-
following
ogy (traffic(1)
locations: site,
themarked
ChineseasAcademy
S1) located of in the southern
Sciences Institute part of the Changchun
of Geography industrial
and Agroecology
zone; (2)site,
(traffic themarked
Liaoyang asResidential
S1) located Areain theinsouthern
the city center
part of(residential
the Changchun site, S2); (3) thezone;
industrial Jilin
Agricultural
(2) the Liaoyang University (campus
Residential Area insite,
theS3)
citysite at the
center southeastern
(residential corner
site, S2); of Changchun;
(3) the Jilin Agricul-
and
tural4)University
the Guangning (campus Village
site, site (suburban
S3) site village, S4), corner
at the southeastern a suburban community
of Changchun; north
and of
(4) the
Guangning Village site (suburban village, S4), a suburban community
Changchun. The locations of these sites are depicted in Figure 1, and detailed descriptions north of Changchun.
The the
and locations of these sites
meteorological are depicted
variables of these in Figure
sites 1, and detailed
are provided in Tabledescriptions
1 and Figure and2, the
re-
meteorological variables of these sites are provided in Table 1 and Figure 2, respectively.
spectively.

Figure
Figure 1.1. Schematic
Schematic map ofof the
the study
studysites
sitesininChangchun
Changchuncity, city, Jilin
Jilin Province,
Province, China.
China. Detail
Detail information
information on meteorology
on meteorology and
and possible
possible emission
emission sources
sources of theof the
sitessites
seenseen at Table
at Table 1. Blue
1. Blue color
color shaded
shaded area
area in the
in the leftleft upper
upper panel
panel indicates
indicates thethe area
area of
of Northeastern
Northeastern China,
China, andand
thetheleftleft lower
lower panel
panel is the
is the wind
wind roserose
mapmap during
during the study
the study period.
period. The The distances
distances between
between the
the sites
sites are indicated.
are also also indicated.

2.2. Filter Sample Collection and Chemical Composition Analysis

Daily 24-h PM2.5 samples were collected at the four sampling sites on 47 mm Whatman
Teflon filters using BGI samplers (Model Omni, BGI Inc., Waltham, MA, USA) at a flow
rate of 5 L/min at about 9 AM local time. The filters were equilibrated in a drying
apparatus (temperature 20–25 ◦ C; RH 35–45%) for 48 h and then weighed with an electronic
balance (Model XS105DU, Mettler Toledo Inc., Greifensee, Switzerland, reading precision
10 µg) before and after sampling. Sampling time, air temperature and air pressure were
automatically recorded, and the standard sampling air volumes (Vstd ) were calculated
from these parameters recorded by the air samplers. The PM2.5 mass concentrations were
Int. J. Environ. Res. Public Health 2021, 18, 4354 4 of 18

calculated using the PM2.5 mass divided by Vstd . Samples were stored below 4 ◦ C in a
refrigerator until analysis to minimize evaporation of volatile components.

Table 1. Description of the sampling sites in this study.

Site Type Geographic Location Description

Southwest of Changchun city, about 30 m north of the 3rd South Ring Road, and
250 m east of the Guigu Street of Changchun city. 24-h aerosol samples were
43◦ 480 38.33” N,
S1 Traffic collected using a PM2.5 sampler, at a height of 3.0 m above the ground in Northeast
125◦ 140 51.20” E
Institute of Geography and Agroecology, Chinese Academy of Sciences. No main
PM sources other than vehicle and road dust were presented at the site.
Northwest of Changchun city, about 200 m west of the 2nd West Ring Road of
Changchun city. The 24-h aerosol samples were collected on an 8-m tall building in
the Liaoyang residential community. Lots of residential buildings and small to
43◦ 530 21.51” N,
S2 Residential medium sizes of stores and restaurants along the streets nearby. A coal-fired boiler
125◦ 160 36.33” E
for heating located about 100 m west of the sampling site. The sources of PM were a
mixture from road and construction dust, coal burning, tailpipe emissions and
food cooking.
Southeast of Changchun city. 24-h aerosol samples were collected using a PM2.5
sampler, at a height of 3.0 m above the ground within the yard of an edible fungi
43◦ 480 28.29” N,
S3 Campus research and teaching in campus of Jilin Agricultural University, about 200 m west
125◦ 240 53.09” E
of the Feihong Road. Fugitive dust and activities related to edible fungi planting
and research may be the main emission sources of PM.
Northwest of Changchun city. 24-h aerosol samples were collected using a PM2.5
sampler, at a height of 3.0 m above the ground in the yard of a farmer’s family in a
Suburban 44◦ 00 41.61” N, village of Lanjia town. The sampler was surrounded by some 5-m high buildings
S4
village 125◦ 150 14.02” E about 10 m away. About 500 m away from the main road of Lanjia Town with many
small factories. Road dust, biomass burning, cooking, and emissions from the
nearby factories in Lanjia Town were the main sources of air pollutants.

A total of 129 filter samples were collected and weighed for bulk PM2.5 mass over the
whole campaign. However, 19 of the samples were accidentally lost before the laboratory
analysis. Consequently, the remaining 110 samples were analyzed for chemical compo-
sitions. For data quality assessment and control (QA/QC), parallel sampling, a blank
test, and a standard curve were performed during the outdoor sampling and laboratory
analysis. For one half of each Teflon filter sample and field blank filter was extracted with
10 mL ultrapure water in an ultrasonic bath for 30 min. After passing through microporous
membranes (pore size 0.45 mm, diameter 25 mm, Auto Science (Tianjin) Instrument Co.,
LTD, Tianjin, China), the extracts were stored at 4 ◦ C in a precleaned tube for analysis. Four
anions (F− , Cl− , NO3 − and SO4 2− ) and 5 cations (Na+ , NH4 + , K+ , Mg2+ and Ca2+ ) were
analyzed by Ion chromatography (ICS-1000, Dionex Inc., Sunnyvale, CA, USA), which
consists of a separation column (Dionex Ionpac AS14 for anion and CS12A for cation) and
a guard column (Dionex Ionpac AG14 for anion and AG12A for cation). A weak base
eluent (3.5 mmol Na2 CO3 /1.0 mmol NaHCO3 solution) was used for anion detection, and
20 mmol methane sulfonic acid (MSA) solution was used for cation detection. Blank values
were subtracted from samples. The recovery rates of the measured ions were in the range
of 80–120%. The limits of detection are in Table S1, and uncertainties are ±10% for all ions.
Int. J. Environ. Res. Public Health 2021, 18, x FOR PEER REVIEW 5 of 20
Int. J. Environ. Res. Public Health 2021, 18, 4354 5 of 18

Figure 2. Temporal variation of PM

Figure 2.5 mass concentration
2. Temporal of 2.5
variation of PM the filter
mass samples at sites
concentration S1filter
of the (a), S2 (b), S3at(c),
samples S4S1
sites (d),
(a),air
S2 (b),
S3 (c), S4
temperature and relative humidity (e),(d),
andairwind
temperature
speed andand relative
wind humidity
direction (e), the
(f) during andsampling
wind speed and wind direction (f)
period.
during the sampling period.
Another half of each Teflon filter sample was dissolved at 170 ◦ C for 4 h in a high-
pressure
2.2. Filter Teflon
Sampledigestion
Collectiontank with mixed
and Chemical acid composed
Composition Analysisof 3 mL of concentrated HNO3 ,
1 mLDaily
of concentrated HClO
24-h PM2.5 samples , and 1 mL of concentrated HF.
4 were collected at the four samplingAfter thesites
solutions
on 47were
mm cooled,
What-
0.1 mL of concentrated HNO 3
man Teflon filters using BGI samplersand deionized water were added to dilute
(Model Omni, BGI Inc., Waltham, MA, USA) the digestion
at a
liquid to 10 mL. A total of 18 elements (Al, Si, Ca, Fe, Mg, K, Mn, Ni, Cu, Zn,
flow rate of 5 L/min at about 9 AM local time. The filters were equilibrated in a drying As, Se, Sr, Ba,
Cd, Cr, Nd,(temperature
apparatus and Pb) were20–25
measured
°C; RHusing an inductively
35%–45%) for 48 h coupled
and thenplasma-atomic
weighed withemission
an elec-
spectrometer (ICPE9000, Shimadzu Co. Ltd., Kyoto, Japan). The sample solutions were
tronic balance (Model XS105DU, Mettler Toledo Inc., Greifensee, Switzerland, reading
measured in triplicate, and standard and blank samples were inserted and analyzed every
precision 10 µ g) before and after sampling. Sampling time, air temperature and air pres-
10 samples for quality control.
sure were automatically recorded, and the standard sampling air volumes (Vstd) were cal-
culated from these parameters recorded by the air samplers. The PM2.5 mass concentra-
tions were calculated using the PM2.5 mass divided by Vstd. Samples were stored below 4
°C in a refrigerator until analysis to minimize evaporation of volatile components.
Int. J. Environ. Res. Public Health 2021, 18, 4354 6 of 18

2.3. Meteorological Data

Meteorological data, including ambient temperature (Ta ), pressure (Pa ), and relative
humidity (RH), were measured using an automatic meteorological station (Model AMS-II-
N, Changchun Meteorological Instrument Research Institute, Changchun, China) at the
IGA site. Wind speed (W s ) and wind direction (W d ) were downloaded from a weather
data archive (http://www.wunderground.com/history; accessed on 16 April 2021).

2.4. Coefficient of Divergence (COD) Analysis

In this study, spatial variability of PM2.5 among the sampling sites were tested through
coefficient of divergence (COD) analysis:
v
!2
p
u
u1 xij − xik
COD jk = t
p ∑ xij + xik
(1)
i =1

where xij and xik represent the 24-h average PM2.5 concentration for day i at site j and site k,
and p is the number of observations. A value of 0 for the COD implies that two sites are
exactly alike, and a value larger than 0 implies that the two sites are dissimilar. Criteria of
COD > 0.2 indicating heterogeneity and <0.1 indicating homogeneity were selected for the
spatial variability analysis of PM2.5 [10,35].

2.5. Enrichment Factor (EF) Analysis for Elements

Here, the enrichment factor (EF) of the chemical elements was calculated to estimate
the relative contributions from natural and anthropogenic sources [10,36,37].

EF = (X/Xref )aerosol /(X/Xref )crust (2)

where (X/Al)aerosol is the ratio of measured concentration of the element of interest (X)
to aluminum (Al) in PM2.5 ; (X/Al)crust is the ratio of X to Al in crustal material. The
information of (X/Al)crust was based on [38].
If the EF values of elements of interest are below 10, their sources are identified as
predominantly natural sources; if the EF values are between 10 and 100, their sources are
believed to be both natural and anthropogenic origins; and if the EF values are larger than
100, the dominance of anthropogenic are confirmed [36].

3. Results and Discussion

3.1. Levels of PM2.5 Concentrations in Wintertime Changchun
The daily average PM2.5 mass concentrations were 122.7 ± 30.9 µg m−3, 136.7 ± 60 µg m−3 ,
137.2 ± 50.1 µg m−3 and 170.6 ± 93.1 µg m−3 at sites S1, S2, S3 and S4, respectively, with
an arithmetic average of 143.5 ± 68.1 µg m−3 for all sites (Figure 2 and Table 2). At all sites,
the PM2.5 levels consistently exceeded the World Health Organization (WHO) air quality
guidelines for PM2.5 (25 µg m−3 ) and China’s Level I and II air quality standards for PM2.5
(35 and 75 µg m−3 , respectively). Our results show that although Changchun is not known
as one of the most polluted cities in China, PM2.5 pollution in Changchun is comparable to
PM2.5 pollution levels in severely polluted Chinese cities such as Beijing [10], Shanghai [39]
and Guangzhou [9], as well as many other polluted Asian cities (Table 3).
As shown in Figure 2 and Table 2, large spatial variabilities in PM2.5 concentrations
existed among the sampling sites. Coefficient of divergence (COD) analysis showed that the
COD values of the site-pairs among the S1, S2, and S3 sites were lower than 0.2, indicating
the spatial variabilities among these sites were small. However, the COD values between
the S4 site and other three sites were all larger than 0.2 (Table S2), indicating the S4 site was
a distinct site among the four sites.
Int. J. Environ. Res. Public Health 2021, 18, 4354 7 of 18

Table 2. Average mass concentrations (mean ± standard deviation) of PM2.5 and corresponding
chemical compositions at four sites.

Chemical S1 S2 S3 S4 Average
Species (µg m−3 )
122.7 ± 30.9 c 136.7 ± 60.0 137.2 ± 51.7 170.6 ± 93.1 143.5 ± 68.1
PM2.5
(76.2–197.0) (54.4–381.4) (65.8–255.6) (48.7–466.0) (48.7–466.0)
7.0 ± 2.9 6.0 ± 4.3 8.0 ± 2.9 11.3 ± 6.0 8.3 ± 5.0
NH4 +
(2.4–11.5) (0.8–19.8) (2.5–15) (3.2–28.6) (0.8–28.6)
1.5 ± 0.2 3.8 ± 1.7 3.1 ± 0.6 2.6 ± 1.2 3.0 ± 1.4
Ca2+
(1–1.7) (1.7–10.4) (2.2–4.6) (1.3–7.4) (1–10.4)
1.5 ± 0.4 2.1 ± 1.3 1.9 ± 0.5 2.6 ± 1.2 2.1 ± 1.1
K+
(0.8–2) (0.9–7) (0.9–3.3) (0.6–5.5) (0.6–7)
1.3 ± 0.4 2.3 ± 0.7 2.1 ± 0.4 1.9 ± 0.7 2.0 ± 0.7
Na+
(0.6–2.3) (1.4–4.7) (1.6–3.1) (1.1–4.3) (0.6–4.7)
0.2 ± 0.1 0.8 ± 0.5 0.6 ± 0.1 0.6 ± 0.4 0.6 ± 0.4
Mg2+
(0.1–0.3) (0.4–3.3) (0.4–1) (0.3–2.5) (0.1–3.3)
7.8 ± 3.5 8.3 ± 5.1 8.9 ± 2.9 10.4 ± 7.1 9.0 ± 5.3
NO3 −
(3–14.5) (0–20.3) (4.6–19.1) (1.1–37.5) (0–37.5)
7.1 ± 3.1 11 ± 4.5 10 ± 3.8 11.1 ± 6.7 10.3 ± 5.1
SO4 2−
(2.2–13.4) (4.5–21.5) (5.4–21.4) (2.2–32.1) (2.2–32.1)
1.11 ± 0.17 0.74 ± 0.28 0.94 ± 0.23 0.95 ± 0.26 0.9 ± 0.28
NO3 − /SO4 2−
(0.77–1.49) (0–1.12) (0.37–1.32) (0.18–1.56) (0–1.56)
4.6 ± 2.1 7.0 ± 1.8 4.5 ± 1.5 10.1 ± 3.8 7.1 ± 3.5
Cl−
(1.7–7.9) (3.2–11.8) (2.3–7.1) (4.1–20.5) (1.7–20.5)
1.0 ± 0.3 3.8 ± 3.7 2.0 ± 1.4 7.3 ± 4.2 4.1 ± 4.0
F−
(0.5–1.8) (0.8–17.3) (0.5–4.5) (1.5–14.8) (0.5–17.3)
39.5 ± 12.9 34.3 ± 11.5 23.4 ± 3.7 28.4 ± 11.1 30.4 ± 11.4
Mineral a
(13.6–57.8) (19.8–55.1) (18.6–31.7) (14.4–75.9) (13.6–75.9)
0.8 ± 0.2 1.3 ± 0.3 0.9 ± 0.1 1 ± 0.5 1.05 ± 0.4
Trace b
(0.5–1) (0.7–2) (0.7–1.3) (0.4–3.4) (0.43–3.42)
n 28 36 28 37 129
a The mineral dust in PM-2.5 was calculated as the sum of oxides of Al, Si, Ca, Fe, Mg, and K (i.e., Mineral dust =
1.89Al +2.14Si +1.40Ca +1.43Fe +1.66Mg +1.21K) [40], of which the concentration of Si was estimated according to
the average ratio of Si/Al (3.6) in earth’s crust [40–42]; b Trace elements include Mn, Ni, Cu, Zn, As, Se, Sr, Ba, Cd,
Cr, Nd, and Pb; c numbers in bold are the average values and standard deviations, and numbers in the brackets
are the observed minimum and maximum values. Site codes seen at Figure 1.

Among the four sampling sites, the suburban (S4) site exhibited considerably higher
PM2.5 concentrations than other sites (Figure 2 and Table 2). The higher PM2.5 level at the
S4 site was likely due to the lack of effective emission control measures for local emission
sources, e.g., coal and biomass burning for household heating and cooking, fugitive dust
from unpaved surfaces, and processes at nearby individual workshops.

3.2. Temporal Variations of PM2.5 Concentrations

During the study period, heavy haze events with PM2.5 levels higher than 150 µg m−3
frequently occurred, as observed on Dec 30 and 31 in 2011 at all the four sites, 26 January 2012
at S2 site, 25 June 2012 at S3 and S4 sites, and 7, 10, 18, 19 January 2012 at S4 site (Figure 2).
A few relatively clean days as observed at S2 and S4 sites were associated with the Chinese
New Year (also known as “Spring Festival”), with the lowest PM2.5 concentration observed
on 21 January 2012, which was Chinese New Year’s Eve.
On 18 and 19 January, a heavy haze occurred simultaneously at S1, S3 and S4 site with
PM2.5 values nearly or higher than 200 µg m−3 . Meteorological analysis (Figure 2) showed
a sudden decrease of wind speeds from 2.8 m/s to 0.8 m/s on 17 January. Meanwhile,
the 48-h back trajectory analysis using the HYSPLIT model [52,53] clearly shows that
the air mass switched suddenly on 17 January from long range transport from southeast
direction to local origins, as could be easily seen by the swift of Above Ground Level (AGL)
of the air mass reaching the sampling site (Figure 3). From January 17 to 20, the static
weather condition, coupled with relatively high air temperature and relative humidity, may
have facilitated the accumulation of air pollutants and generation of secondary aerosols,
resulting in the dramatic increasing of PM2.5 concentrations.
Int. J. Environ. Res. Public Health 2021, 18, 4354 8 of 18

Table 3. Comparison of PM2.5 and PM10 mass concentrations in Northeastern China with other regions.

PM10 PM2.5 Measuring

City Station Type Year Season/Period Reference
(µg m−3 ) (µg m−3 ) Method/Instrument
Northeastern China
Teflon filter
Changchun Urban 2012 Winter 132.6 ± 50.6 This study
gravimetric method
Teflon filter
Rural 2012 Winter 170.6 ± 93.6 This study
gravimetric method
Quartz filter
Urban 2003 Winter 140.5 ± 28.6 [43]
gravimetric method
Quartz filter
Urban 2014 Autumn 146.0 ± 107.0 [31]
gravimetric method
Urban 2018 Winter 121.8 ± 101.7 APDA-375A [29]
Sartorius MC5
Baicheng Semi-arid 2006 Spring 260.9 ± 274.4 [23]
electronic microbalance
Winter Quartz filter
Harbin Urban 2008–2009 308 ± 167 [26]
(haze episode) gravimetric method
Quartz filter
Urban 2006–2007 Winter 155.1 [44]
gravimetric method
Quartz filter
Rural 2006–2007 Whole year 81.8 [45]
gravimetric method
Urban 2010–2012 Winter 88.0 ± 23.5 69.5 ± 19.9 GRIMM180 [27]
Shenyang Teflon filter
Urban 2004–2005 Winter 132 [24]
gravimetric method
Other region of China
Beijing Urban 2005–2007 Winter 91 (63–112) TEOM a [46]
Teflon filter
Urban 2010 Winter 139 ± 86 [10]
gravimetric method
Glass filter
Shanghai Urban 2009–2010 Winter 122 [39]
gravimetric method
Guangzhou Urban 2004 Autumn 153.9 ± 52.1 TEOM (1400) [9]
Quartz filter
Xi’an Urban 2006 Winter 266.8 [47]
gravimetric method
Other countries
Teflon filter
Ulaanbaatar Urban 2008 Winter 105.1 ± 34.9 [48]
gravimetric method
New Delhi Urban 2011 Whole year 122.3 ± 90.7 C14 BETA (FH 62 C14) [49]
Winter Quartz filter
Bangkok Urban 2010 55 (16–103) [50]
(dry season) gravimetric method
Reno Urban 2008–2010 Winter 15 (2–18) BAM b [51]
a TEOM: Tapered Element Oscillating Microbalance; b BAM: beta attenuation monitor.

Over the whole campaign, correlation analysis (Figure S1) indicated that PM2.5 showed
strong negative relationship with visibility, suggesting important influences of PM2.5 on
haze pollution. Besides, PM2.5 showed an obvious negative correlation with wind speed
owing to the dilution effects of wind on PM2.5 in the atmosphere. However, no obvious
correlations were observed between PM2.5 and air temperature, relative humidity, dew
point temperature and air pressure. Further analysis showed that the heavy hazy days
were usually associated with winds from the directions of potential main emission sources
as depicted in Table 1 (also see Figure S2).
 Int. J. Environ. Res. Public Health 2021, 18, x FOR PEER REVIEW 10 of 20
Int. J. Environ. Res. Public Health 2021, 18, 4354 9 of 18

Figure3.3.The
Figure The evolution
evolutionof
of48-h
48-hbackward
backwardtrajectories
trajectoriescommencing
commencingatat12:00
12:00(local
(localtime)
time)on
on15
15through
through
21 January 2012 at Changchun (43.89 N, 125.28 E) during which a haze event occurred
21 January 2012 at Changchun (43.89 N, 125.28 E) during which a haze event occurred on 18 on 18 and 19
and
January. The evolution of the trajectories is indicated by dates at the ends of the trajectories. The
19 January. The evolution of the trajectories is indicated by dates at the ends of the trajectories. The
numbers in the brackets are PM2.5 mass concentrations at the S4 site for each day. The black lines in
numbers in the brackets are PM2.5 mass concentrations at the S4 site for each day. The black lines in
the lower panel are the terrain heights where the trajectories passed over.
the lower panel are the terrain heights where the trajectories passed over.
There is a distinctive temporal changes in PM2.5 at the residential (S2) site compared
There is a distinctive temporal changes in PM2.5 at the residential (S2) site compared to
other sitessites
to other (Figure
(Figure 2). The
2). The PMconcentrations
PM2.5 2.5 concentrations at the S1 and S4 sites decreased remark-
at the S1 and S4 sites decreased remarkably
ably after 21 January, which
after 21 January, which was possiblywas possibly related
related to the
to the reduction
reduction ofofsecondary
secondaryinorganic
inorganic
aerosols (Figure 4d). However, the PM 2.5 levels at site S2 increased noticeably during the
aerosols (Figure 4d). However, the PM2.5 levels at site S2 increased noticeably during
same
the period,
same largely
period, duedue
largely to the
to increase
the increase of mineral dust dust
of mineral (Figure 4b). As
(Figure 4b).shown in Figure
As shown in
5, the elements related to crustal (e.g., Al, K, and Sr), motor vehicles (e.g.,
Figure 5, the elements related to crustal (e.g., Al, K, and Sr), motor vehicles (e.g., Pb and Pb and Zn), coal
combustion
Zn), (e.g., As) (e.g.,
coal combustion and fireworks (e.g., Sr) also
As) and fireworks increased
(e.g., Sr) also considerably after 21 January,
increased considerably after
indicating that human activities in the residential area during
21 January, indicating that human activities in the residential area during the Chinese Spring Festival
the Chinese
celebration
Spring maycelebration
Festival have appreciably
may have contributed
appreciably to contributed
local PM2.5 pollution
to local PM at2.5
the S2 site, at
pollution re-
gardless of the intrusion of cleaner background air.
the S2 site, regardless of the intrusion of cleaner background air.

3.3. Chemical Compositions of PM2.5

At all sites, mineral dust was the most abundant chemical component, contributing
13.6 µg/m3 to 75.9 µg/m3 to PM2.5 mass concentration, with an arithmetic average of
30.4 ± 11.4 µg/m3 (Table 2). Here the mineral dust in PM2.5 was calculated as the sum
of Al, Si, Ca, Fe, Mg and K oxides (i.e., mineral dust = 1.89 Al +2.14 Si +1.40 Ca +1.43 Fe
+1.66 Mg +1.21 K) [40], assuming that the elements existed as oxides [54]. In this study,
the mineral levels were much comparable to those reported in other Chinese cities (e.g.,
26.5 µg/m3 in Beijing [10]) and constituted the largest portion (20.7%) of total PM2.5 mass,
indicating prevailing emission of soil dust particles in Changchun.
Int. J. Environ. Res. Public Health 2021, 18, x FOR PEER REVIEW 11 of 20
Int. J. Environ. Res. Public Health 2021, 18, 4354 10 of 18

Figure 4.
Figure Temporal variations
4. Temporal variations of
of mass
massconcentrations
concentrationsofofthe
themineral
mineraland secondary
and secondary inorganic aerosols
inorganic aero-
(SO 2− , NO − , −and NH ++) in the daily PM samples at sites S1 (a), S2 (b), S3 (c), and S4 (d).
sols 4(SO4 , NO
2−
3 3 , and NH 4 4 ) in the daily PM2.5
2.5 (c), and S4 (d)

The secondary inorganic aerosols (SIA, including SO4 2− , NO3 − and NH4 + ), with a
mean of 27.6 ± 5.2 µg/m3 , constituted the second largest portion (18.8%) of the total PM2.5
mass. This percentage was lower than some reported values in Beijing (28%) [8], Tianjin
(34.1%) [36], and Guangzhou (48.5%) [55], but similar to or even higher than those in some
other studies conducted in wintertime Beijing (12.0% in [10] and 20.5% in [55]), Harbin
(13.7%) [56], and Changchun (18.7%) [31]. We suggest that the relatively low SIA/PM2.5
mass ratios in this study might indicate that the low temperatures in such cold regions
have suppressed secondary inorganic formation in winter.
Another notable feature of the chemical characteristics of PM2.5 in the study period
is high Cl− (7.1 ± 3.5 µg/m3 ) and F− (4.1 ± 4.0 µg/m3 ) loadings at all sites. To our
knowledge, the observed F− content (7.3 ± 4.2 µg/m3 ) at the suburban site (S4) was the
highest value ever reported at an urban environment based on literatures. F− concentration
typically ranges from 0 to 2 µg/m3 [57,58]. Cl− and F− are usually emitted from coal
combustion [57], while Cl− can also be emitted from biomass burning in NE China [59].
Although coal burning is important in Changchun due to domestic heating, the unusually
high levels of Cl− and F− concentrations could not be accounted for by coal burning
alone because other co-emitted components [60] were not elevated proportionally. After
examining the local emission sources, we speculate that the high levels of F− observed
in this study can be attributed to emissions from plastic-making and specialized glass-
making facilities near the S4 site, where glass products were treated with an F solution for
embroidery designs. Additionally, NH4 + at S4 was the highest among the four sites, likely
due to its proximity to NH3 emission sources such as poultry farms.
 Int. J. Environ. Res. Public Health 2021, 18, x FOR PEER REVIEW 12 of 20
Int. J. Environ. Res. Public Health 2021, 18, 4354 11 of 18

Figure 5. Temporal variations of mass concentrations of the representative ions and elements in the daily PM2.5 samples.
Figure 5. Temporal variations of mass concentrations of the representative ions and elements in the daily PM2.5 samples.
Among the trace elements, As (0.7 ± 0.2 µg/m3 ), Zn (0.65 ± 0.4 µg/m3 ) and Ba
3 ) were the most abundant in PM . As is a marker for coal combustion and
3.3.±Chemical
(0.3 0.2 µg/m Compositions of PM2.5 2.5
was present at much higher levels in this study
At all sites, mineral dust was the most abundant than in other studies
chemical [61], suggesting
component, that
contributing
wintertime air pollution in Changchun may pose serious health threats to local
13.6 µ g/m3 to 75.9 µ g/m3 to PM2.5 mass concentration, with an arithmetic average of 30.4 ± residents
given
11.4 µthe
g/mwell-known health
3 (Table 2). Here theeffects associated
mineral dust in with
PM2.5such
was trace elements.
calculated as theZn andofBa
sum Al,are
Si,
associated with non-tailpipe emissions, such as brake and tire wear [62].
Ca, Fe, Mg and K oxides (i.e., mineral dust = 1.89 Al +2.14 Si +1.40 Ca +1.43 Fe +1.66 Mg Ba is also a
good indicator of firework emissions [63,64]. The Zn concentrations observed
+1.21 K) [40], assuming that the elements existed as oxides [54]. In this study, the mineral in this
study
levelsare comparable
were to those to
much comparable inthose
polluted citiesin
reported such asChinese
other Shanghai [65](e.g.,
cities and 26.5
the Beijing–
µ g/m3 in
Tianjin–Shijiazhuang city clusters [66] in China. Whereas the observed Ba concentration is
Beijing [10]) and constituted the largest portion (20.7%) of total PM2.5 mass, indicating pre-
much higher than those reported in the Beijing–Tianjin–Shijiazhuang city clusters [36,66],
vailing emission of soil dust particles in Changchun.
indicating contribution from fireworks emissions.
The secondary inorganic aerosols (SIA, including SO42−, NO3− and NH4+), with a mean
of 27.6
3.4. ± 5.2 Variations
Temporal µ g/m3, constituted the second largest portion (18.8%) of the total PM2.5 mass.
of PM2.5 Components
This percentage was lower than some reported values in Beijing (28%) [8], Tianjin (34.1%)
For the S4 site, high SIA loadings on 18 and 19 January, and a sudden falling of SIA on
[36], and Guangzhou (48.5%) [55], but similar to or even higher than those in some other
21 January were observed (Figure 4). We attributed such changes to both regional-scale
studies conducted in wintertime Beijing (12.0% in [10] and 20.5% in [55]), Harbin (13.7%)
transport and secondary formation processes from local precursors. From 17 to 19 January,
[56], and Changchun (18.7%) [31]. We suggest that the relatively low SIA/PM2.5 mass ratios
the dominating air masses were from local origins (Figure 3) which provided a meteoro-
in this study might indicate that the low temperatures in such cold regions have sup-
logical condition (low wind speed and high ambient temperature and humidity) that was
pressed secondary inorganic formation in winter.
favorable to growth and accumulation of SIA [67]. After three days of accumulation, SIA
reached the maximum value on 19 January. Meanwhile, on 21 January, the dominating air
Int. J. Environ. Res. Public Health 2021, 18, 4354 12 of 18

mass origins switched to remote regions as far as Russia. Such air masses provided clean
background air and a meteorological condition in favor of diluting the pollutants, resulting
in a sudden decrease of SIA and total PM2.5 mass.
After 21 January, the mineral components increased notably at the residential (S2)
site but decreased at other sites (Figure 5). The opposing temporal trends of mineral
contents between S2 and other sites resulted in differences in PM2.5 trends between these
sites, as mentioned above (Figure 2). The increase in crustal components at site S2 was
unlikely to have been caused by windblown dust emissions from the strong wind during
this period or by long-range transport of dust plumes from northern arid lands. During
the campaign period, the surface in northern China was largely covered by snow and
ice, and soil moisture was too high to allow dust mobilization. Long-range transport was
also excluded because only the S2 site observed increased crustal element concentrations,
whereas other sites that were likely influenced by dust plumes did not experience increases
in crustal elements. Emissions from local sources, including fireworks and bridge and
subway construction, resumed after the holidays in urban areas. In addition, fugitive dust
was re-suspended by human activities under windy conditions. These factors were the
major reasons for the increase in crustal PM2.5 concentrations at the S2 site.
Figure 5 illustrates the temporal variations of the measured ions other than SIA and
crustal elements. In general, these elements showed larger variations at the S2 and S4 sites
than at the other locations, which is consistent with the variable trends in PM2.5 concentra-
tions. Site S2 exhibited high loadings of mineral elements (e.g., Al, K), coal ash indicators
(e.g., As) and firework indicators (e.g., Sr) after 21 January, which is consistent with the
aforementioned temporal trends of mineral PM2.5 (Figure 4) and overall PM2.5 (Figure 2).
The S4 site exhibited extremely high values for almost all elements on 30 December, the
day with a very high PM2.5 value (321 µg m−3 ). However, high ion and element loadings
were not detected on the next day (31 December) when the PM2.5 concentration peaked
(reaching 463 µg m−3 ), suggesting that the peak was caused by different emission sources
than those on the previous day. The abrupt changes in PM2.5 concentrations and chemical
compositions highlighted the complexity associated with understanding the sources and
behaviors of aerosol pollution in this area.

3.5. Source Characteristics of PM2.5

As shown in the above sections (Table 2; Figure 2), in conjunction with COD analysis,
large spatial variabilities in PM2.5 concentrations were observed among different locations,
suggesting different source origins of PM2.5 at different locations. Among the sampling
sites, the S2 site and especially the S4 site showed obvious distinction. The large spatial
variations in PM2.5 might come from a couple of causes: (1) The samples over the campaign
were sparse, resulting in limited number of pairs ranging from 24 to 33 and thus larger
COD values; (2) The sampling sites were far from each other (9–14 km) and characterized
with significantly different surroundings, which increased spatial variabilities of PM2.5 ;
(3) Contributions from primary emission sources, i.e., mineral dusts (20.7%), were relatively
more important than those from secondary inorganic aerosols, i.e., SIA (18.8%), causing
sensitive responses of PM2.5 to primary sources and thus relatively large spatial variabilities.
Indeed, four sampling sites were far less than needed to fully represent the spatial vari-
abilities of PM pollution in such a metropolitan region with a fully urbanized area larger
than 1200 km2 (https://en.wikipedia.org/wiki/Changchun; accessed on 16 April 2021).
Actually, nine sampling stations in urban area and one station in outer suburb have been in
running by Bureau of Ecology and Environment of Changchun since 2013.
From the results of chemical analysis (Table 2; Figures 4 and 5), and the constructed
mass closure of PM2.5 (Figure 6), the PM2.5 sources of the sampling sites also showed
obvious spatial variabilities. For example, the S1 site showed highest mineral components
and NO3 − /SO4 2− mass ratio, consistent with its source features as influenced significantly
by traffic; the S2 site showed high SO4 2− , As and mineral, indicating the prominent
contributions from coal burning and traffic; the S4 site was characterized by high halogen
 Int. J. Environ. Res. Public Health 2021, 18, 4354 13 of 18
Int. J. Environ. Res. Public Health 2021, 18, x FOR PEER REVIEW 15 of 20
Int. J. Environ. Res. Public Health 2021, 18, x FOR PEER REVIEW 15 of 20
species, K+ and NH4 + , indicating the contributions from multi-sources such as coal burning,
glass sculpture, biomass burning, and agricultural sectors.

Figure 6. Pie-chart showing the chemical compositions (in %) of PM2.5 mass concentrations for the
Figure 6. Pie-chart showing the chemical compositions (in %) of PM2.5 mass concentrations for the
Figure 6.
sampling Pie-chart showing the chemical compositions (in %) of PM2.5 mass concentrations for the
sites.
samplingsites.
sampling sites.
TheTheenrichment factor (EF) analysis for the elements was also used to estimate the
enrichment factor (EF) analysis for the elements was also used to estimate the rela-
relative The enrichment factor (EF)
andanalysis for the elements was also usedPMto 2.5 estimate
in Chang-the
tive contributions ofofnatural
contributions natural and anthropogenic
anthropogenic origins
origins toto wintertime
wintertime PM 2.5 in Changchun,
relative
chun, contributions
following of natural and anthropogenic origins(Figure
to wintertime PM2.5 in Chang-
following thethe methods
methods developed
developed by [38].
by [38]. TheThe results
results (Figure 7) show7) show
thatthat
the the cal-
calculated
chun,EF
culated following
values the
of Al,methods
Si, Fe, developed
Mn, K, Mg, by [38].
Ca, and Thewere
Na results
all (Figure
below 7) show
10, suggestingthat the cal-
that
EF values of Al, Si, Fe, Mn, K, Mg, Ca, and Na were all below 10, suggesting that these
culated
these EF
elements values
came of Al, Si, Fe,
predominantly Mn, K,
from Mg, Ca,
natural and Na
sources. were all below 10, suggesting that
elements came predominantly from natural sources. TheThe EF values
EF values ofCu,
of Ba, Ba, Cr,
Cu,Ni,
Cr,and
Ni, Pb
andthese
Pb elements
were came10predominantly
between and 100, from natural
suggesting sources.from
contributions The both
EF values
naturalof Ba,
and Cu, Cr, Ni,
anthro-
were between 10 and 100, suggesting contributions from both natural and anthropogenic
and Pbsources.
pogenic were between
The EF10 and 100,Zn
values suggesting contributions from
100,both naturalthe anddomi-
anthro-
sources. The EF values of Znofand andwere
As As were
largerlarger than
than 100, indicating
indicating the dominance of
pogenic
nance sources.sources
of anthropogenic
anthropogenic
The sources
EFsuch
values of Zn
such
as
and Ascoal
as traffic,
traffic,
were
coal burning,
larger
burning, than 100,processes.
indicating
and industrial
and industrial
the domi-
processes.
nance of anthropogenic sources such as traffic, coal burning, and industrial processes.

Figure 7. Enrichment factors calculated using Al as a reference element during the whole sam-
Figure 7. Enrichment factors calculated using Al as a reference element during the whole sampling
Figureperiod.
pling
period. 7. Enrichment factors calculated using Al as a reference element during the whole sampling
period.
 In summary, the PM2.5 sources in Changchun were characterized with high spatial
variabilities among different sites and noteworthy contributions from mineral and halo-
gen species (Figure 6). In addition, the EF analysis showed high EF values of the As ele-
ment.
Int. J. Environ. Res. Public Health 2021, 18, 4354 The chemical and source characteristics of PM2.5 were consistent with Changchun
14 of 18
as being a typical coal burning and industry city.

3.6. In
Implications
summary,forthethePMEffectiveness
2.5 sourcesofinHaze Pollutionwere
Changchun Control Measures with high spatial
characterized
variabilities amongthe
To estimate different sites and
effectiveness ofnoteworthy contributions
haze mitigation measuresfrom mineral
dating backand halogen
to 2012, his-
species (Figure
toric air 6).data
quality In addition, the EF analysis
in Changchun showed
from Chinese high EF values
Environmental of theAgency
Protect As element.
were
The chemical
collected and source characteristics of PM2.5 were
(https://www.aqistudy.cn/historydata/; consistent
accessed on with Changchun
16 April as beingin
2021). Results
aFigure
typical8coal burning and industry city.
show that wintertime PM2.5 pollution was very severe in 2012 and 2013, and de-
creased significantly in 2014 after implementing the new Chinese National Ambient Air
3.6. Implications for the Effectiveness of Haze Pollution Control Measures
Quality Standard (NAAQS) in 2013, but still stayed above Level II (75 μgm−3) of NAAQS.
ThereTo was
estimate the effectiveness
an obvious decreasing of trend
haze mitigation measures
in both annual dating
averages back
and to 2012, historic
wintertime level of
air quality data in Changchun from Chinese Environmental Protect Agency were
PM2.5 from 2013 to 2018, synchronizing well with the implementation of major air quality collected
(https://www.aqistudy.cn/historydata/; accessed on 16ofApril
control and prevention measures, i.e., implementation NAAQS 2021). Results
in 2013, in Figure
Action Plan 8of
show that wintertime PM 2.5 pollution was very severe in 2012 and 2013,
Air Pollution Prevention and Control in 2014, Clean Air Action Plan in 2016 and Three-and decreased
significantly
Year Blue Sky in 2014
War after implementing
in 2018. the new Chinese
Such synchronization probablyNational Ambient
indicated Airmeasures
that the Quality
Standard (NAAQS) in 2013, but still stayed above Level II (75 µgm −3 ) of NAAQS. There
taken by local government had exerted remarkable effects in cutting down the fine particle
was an obvious decreasing trend in both annual averages and wintertime level of PM2.5
pollution in the Changchun area.
from 2013 to 2018, synchronizing well with the implementation of major air quality control
However, the PM2.5 switched to a slightly increasing trend from 2019. Even more, the
and prevention measures, i.e., implementation of NAAQS in 2013, Action Plan of Air
wintertime PM2.5 in the period between 23 December 2019 and 31 January 2020 reached
Pollution Prevention and Control in 2014, Clean Air Action Plan in 2016 and Three-Year
the highest level since 2014. The PM2.5 level appears to reach a stationary plateau stage,
Blue Sky War in 2018. Such synchronization probably indicated that the measures taken by
with PM2.5 loadings ranging between 51 and 56, and greater efforts must be made to fur-
local government had exerted remarkable effects in cutting down the fine particle pollution
ther lower the pollution level in the future.
in the Changchun area.

Figure 8. Long-term variations of PM2.5 concentrations in periods from 23 December to 31 January next year (box plots),
Figure 8. Long-term
year-round averages ofvariations of PM2.5 concentrations
PM2.5 concentrations (solid green in periods
line), from published
and other 23 DecemberPMto
2.5 31 January nextfrom
concentrations yearFang
(box et
plots),
al.,
year-round
2017 averages
(pink triangle) andofBai
PMet concentrations
2.5 al., 2020 (orange(solid
star).green line),
Letters andthe
below other published
x axis indicatePM 2.5 concentrations
related from
events: a. The Fang et al.,
observation
2017 (pink
campaign wastriangle) and from
conducted Bai et23 al.,December
2020 (orange
2011star).
to 31 Letters
Januarybelow the xstudy);
2012 (this axis indicate related events:
b. Implementation of a.
theThe observation
new released
campaign was conducted from 23 December 2011 to 31 January 2012 (this study); b. Implementation of the new released
China’s Air Quality Standard in 2013, which included PM2.5 as a new criterion pollutant for the first time; c. Action Plan of
China’s Air Quality Standard in 2013, which included PM2.5 as a new criterion pollutant for the first time; c. Action Plan
Air Pollution Prevention and Control in 2014.6; d. Clean Air Action Plan in 2016.7; e. Three-Year Blue Sky War in 2018.9;
of Air Pollution Prevention and Control in 2014.6; d. Clean Air Action Plan in 2016.7; e. Three-Year Blue Sky War in 2018.9;
f. f.The
Theday
day(23
(23January
January2020)
2020)when
whenWuhan,
Wuhan,China
China released
releasedannouncement
announcement ofof
lock-down
lock-down due
due toto
the COVID-19
the COVID-19 epidemic.
epidemic.

However, the PM2.5 switched to a slightly increasing trend from 2019. Even more, the
wintertime PM2.5 in the period between 23 December 2019 and 31 January 2020 reached the
highest level since 2014. The PM2.5 level appears to reach a stationary plateau stage, with
PM2.5 loadings ranging between 51 and 56, and greater efforts must be made to further
lower the pollution level in the future.
Int. J. Environ. Res. Public Health 2021, 18, 4354 15 of 18

4. Conclusions
This study presents detailed field observations of the chemical components and spatio-
temporal variations of wintertime PM2.5 in the Changchun metropolitan area located
in the center of the China’s breadbasket region. Such information could be used as a
baseline for related studies based on the fact that such information for this region was
very limited before 2013. We found that severe wintertime haze pollution existed in
Changchun due to unique environmental settings, including strong temperature inversion,
high emission loadings, scattered sources with mixed fuel types, and frequent use of
deicing salts. Observations from the four sites across the city revealed that PM2.5 levels
(143 µg m−3 ) constantly exceeded the WHO air quality guidelines for PM2.5 (25 µg m−3 )
and China’s Level I (35 µg m−3 ) and II (75 µg m−3 ) air quality standards for PM2.5 , with
levels comparable to those observed in Asia’s most polluted cities. Mineral dust and
secondary inorganic aerosols together contributed about 40% to the total PM2.5 mass.
While strong dependence of PM2.5 levels on atmospheric circulation were found, the
observed heterogeneous distribution of PM2.5 mass and chemical compositions among
the monitoring sites suggested that localized emission sources significantly affected PM2.5
pollution in Changchun. In particular, the suburban village site exhibited the highest PM2.5
levels and extremely high Cl− and F− loadings.
Results from this study shed light on both the severity of air pollution in China
and the potential measures required to understand and mitigate air pollution in this
region. The fact that the levels of both total PM2.5 and its inorganic components were
comparable to those in China’s most polluted cities was surprising because Changchun
has generally been considered less polluted than other large Chinese cities. In fact, the
sky was blue and sunlight was dominant during the field campaign, even on the most
polluted days, unlike the visible haze in other cities. However, pollution was visible from
a horizontal viewpoint. Our results suggest that there is likely a mechanism behind the
high pollution episodes in this region that is distinct from the mechanisms in the Beijing–
Tianjing–Hebei region or the Pearl River Delta region. The distinct characteristics of air
pollution in this region also make pollution difficult to detect using satellite remote sensing
or to simulate using numerical chemical transport models. The shallow boundary layer
confines most of the aerosols to the lowest atmospheric layer, and the land in this region is
largely covered by snow and ice during the cold season, making it challenging to remotely
sense atmospheric aerosols. Furthermore, emission inventories in China have focused
on typical industrial sources derived from province-level [68] or county-level [69] energy
consumption. Chemical transport models based on these inventories are likely to under-
predict some major components of PM2.5 unless the missing sources can be accurately
accounted for in the emission inventories used to drive these models.
Based on the results of the chemical component analysis, one notable characteristic of
air pollution in wintertime Changchun was high loadings of mineral dust, other than the
chemical species related to the burning of fossil fuels. Thus, effective measures, i.e., more
thorough and frequent sweeping or watering of streets, covering of bare soil on sides of
busy roads, and stricter dust controls for the widespread construction activities, should be
taken to control the road and off-road dust emissions. In addition, the comparisons among
the monitoring sites showed that the upwind suburban sites were more polluted than the
sites in the urban area. In the future, more attention should be paid to the emissions from
small factories of the township enterprises in the suburban and even rural areas.

Supplementary Materials: The following are available online at https://www.mdpi.com/article/10

.3390/ijerph18084354/s1, Figure S1: Correlation relationships between filter based PM2.5 and related
meteorological factors, Figure S2: Contouring plot showing the relationship between measured PM2.5
and wind speed and direction for the four sampling sites., Table S1: Method detection limit (MDL)
for measuring the concentrations of 9 ions and 18 elements, Table S2: Coefficients of Divergence
(COD) and pearson correlation analysis for the bulk PM2.5 concentrations between site pairs.
Int. J. Environ. Res. Public Health 2021, 18, 4354 16 of 18

Author Contributions: Conceptualization, S.Z. and D.Q.T.; methodology, M.D., W.C. and X.Z.;
investigation, W.C. and H.Z.; writing—original draft preparation, S.Z.; writing—review and editing,
D.Q.T., X.P. and Y.W.; visualization, B.S.; supervision, M.D.; project administration, S.Z.; funding
acquisition, S.Z. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the National Key R & D Program of China, grant number
2017YFC0212301 and the National Natural Science Foundation of China, grant number 41575129.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are within the article or supplemen-
tary materials.
Acknowledgments: Authors gratefully thank anonymous reviewers for their extensive knowledge
and helpful advice. We thank Qi Zhang and the Beijing Municipal Institute of Labor Protection for
measuring the ions and elements in the samples in this study.
Conflicts of Interest: The authors declare no conflict of interest.

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