Aerosol and Air Quality Research, 16: 1366–1377, 2016

Copyright © Taiwan Association for Aerosol Research

ISSN: 1680-8584 print / 2071-1409 online
doi: 10.4209/aaqr.2015.05.0294 

Source Identification of Acid Rain Arising over Northeast China: Observed

Evidence and Model Simulation

Baozhu Ge1, Zifa Wang1*, Alex E. Gbaguidi2, Qingxin Zhang3

1
State Key Laboratory of Atmospheric Boundary Layer Physics and Atmospheric Chemistry, Institute of Atmospheric
Physics, Chinese Academy of Sciences, Beijing 100029, China
2
AECOM-Asia, Hong Kong
3
Liaoning Environmental Monitoring & Experiment Center, Liaoning, China

ABSTRACT

Acid rain has already been the environment issue for the past century and is still concerned in Southern and Eastern
China. However, Northeastern China, considered in the past as non-acid rain area, is reported high frequency of acid rain
occurred recently. Through a measurement and model simulation analysis with linear regression technique, factor
speciation, backward trajectory, source-tracing and fraction sampling methods, this study aims to investigate the causes of
the acid rain frequently occurred in the two Northeastern cities (i.e., Dandong and Dalian) and to identify the contributing
sources of the chemical ions in precipitation. The annual averaged pHvwa of 2007 ranged within 4.15–4.27 and 4.5–5.15
over Dandong and Dalian, which suggested the similar acidity with Southern China. The precipitation acidity in Dandong
was found to be sulfur dominant in winter-spring (nssSO42–/NO3– = 13.1) than summer-autumn (nssSO42–/NO3– = 1.05),
whereas in Dalian, estimated ratio nssSO42–/NO3– was about 2.35 all over the year, reflecting the strong impact of local
NOx emissions from a much more intense mobile traffic in comparison with Dandong. The findings also revealed a typical
physico-chemical condition with constant strong influence of regional transport over Dandong and Dalian particularly in
summer. Besides, analysis of washout and rainout mechanisms showed that the long range transport in-cloud (rainout) was
more pronounced in Dandong (with minor local emissions) than Dalian (with more significant local emissions). This study
indicates that acid rain pollution in Northeastern China requires much effort, not only in local emission abatement, but also
in regional trans-boundary pollution control.

Keywords: Acid rain; Northeast China; Precipitation chemistry; Scavenge; Source identification.

INTRODUCTION Nevertheless, in order to improve the knowledge on acid

Acid rain has been one of the most cross-cutting and
challenging environmental issues in the past half a century
in China (Larssen et al., 2006). Actually, rapid economic
development and population growth resulted in increasing
emissions and subsequently potential deposition of acidic
substances and widespread acid rain in southern China
between the 1980s and the mid-1990s (Wang and Wang,
1996; Ding et al., 1997; Ding et al., 2004). To conquer the
problem, China had developed the concept of the acid-rain
control zone as the main framework for setting priorities in the
acid-rain reduction policy. The policy for acid-rain mitigation
used a flat emission reduction goal of 20% from 1995 to 2010
within the acid-rain control zone (Larssen et al., 2006).
*
Corresponding author.
Tel.: 86-10-82084278; Fax: 86-10-62041393
E-mail address: zifawang@mail.iap.ac.cn
rain and resulting effects in China, a great need still persists
for better control of the environmental degradations. Based
on the latest 15 years observations (1992–2006) of the acid
rain network, statistics and analysis results showed that the
acid rain still dominated in the vast regions south of the
Yangtze River, with an obvious expanding tendency of acid
rain zones in central and northern China where alkaline dust
from the desert areas, cement production, and construction
activities largely neutralized the acids in the past (Annual
report of CAMS, 2009;Xie et al., 2009; Tang et al., 2010;
Ge et al., 2011). More recently, acid deposition rate in
Northeast China strongly increased since 2004, especially
in Liaoning Province identified as one of the most affected
areas (Hong et al., 2009; Yang et al., 2012a; Zhang et al.,
2012; The Liaoning Environmental Bulletin Report in 2007:
http://www.lnepb.gov.cn/zfxxgk/hjzl/hjzlzkgb/201011/t201
01111_19082.html). According to The Liaoning
Environmental Bulletin Report in 2007, increasing trends
of acid rain frequency ranging from 1.3% in 2001 to 9.7%
in 2007 have been observed over the province. Monitored
 Ge et al., Aerosol and Air Quality Research, 16: 1366–1377, 2016  1367
precipitation chemistry and pH values (rain water pH <
4.5) in 2007 revealed a severe acid rain over the Province
where Dandong and Dalian cities were reported as the most
affected cities with the lowest acid neutralization capability
despite weak local acid precursor emissions (Hong et al.,
2009; Zhang et al., 2012). Thereby, as underlined by Zhang
et al. (2012), elucidating the role of the regional chemical
transport, and more importantly, the contrasting critical
lower precipitation pH and higher neutralizing capability
between downtown and rural areas, remains crucial for
environmental implications in Dalian and Dandong cities.
Based upon the measurement analysis with linear
regression technique, factor speciation, backward trajectory
and fraction sampling methods, as well as source-tracing
simulation method, this study aims to specify the
contributing regional sources to the chemical components
of the precipitation over Dandong and Dalian cities, where
the high frequency acid rain often occurred. The main
purpose is to delve into the regional physico-chemical
pathways of acidification process over Northeastern China.
In collaboration with Liaoning Environmental Monitoring
Center, this work is expected to provide valuable insights
for policy makers in reducing environmental burden in
Liaoning Province.
EXPERIMENT AND METHOD
Measurement Sites
Fig. 1 shows the observation sites located in Dandong
and Dalian in Liaoning Province. Dalian is a coastal city
with a population of more than 50 million, which could be
identified as an area influenced by anthropogenic emissions
mainly from shipbuilding industry, traffic, petrochemical
Fig. 1. The Measurement Stations in Dalian and Dandong (marked in red).
industry and the big power plant in surrounding areas (Kong
et al., 2010; Zhang et al., 2012). There are three sites in
Dalian; one is a rural site located in the southeast of Dalian
(Lvshun, abbrev LS, Number 1th in Fig. 1) and the other two
are unban sites, located in the HeiShiJiao Park (Heishijiao,
abbrev HSJ, Number 2th in Fig. 1) and in the industry zone
(Ganjinzi, abbrev GJZ, Number 3th in Fig. 1). In Dandong,
where is more influenced by framing rather than industrial
activities, there are two sites (one rural, Langtou abbrev LT
Number 4th and one urban Jiancezha, abbrev JCZ, 5th in
Fig. 1).
Sampling Analysis and Quality Control
In 2007, sixty five and seventy samples were collected
as a daily frequency in Dandong and Dalian respectively
for measurement of nine key chemical species, pH and
conductivity. The number of samples in winter, spring,
summer and autumn are 6, 18, 29 and 12 for Dandong and
2, 20, 34 and 14 for Dalian, respectively. Besides, the
sequential sampling during June and July of 2009 in JCZ,
HSJ and GJZ were also measured with four, two and three
events, respectively. The pH and the electrical conductivity
(EC) of rainfall were measured by Glass electrode pH meter
(AR20, Thermo Fisher Scientific Inc.) and EC meter (HI9032,
HANNA) immediately. The collected rainfall samples had
been refrigerated under 0°C–4°C and analyzed in the
laboratory. Four anions (SO42–, NO3–, Cl–, F–) and five
cations (NH4+, Na+, K+, Ca2+, Mg2+) were quantitatively
measured by ion chromatography (IC, Dionex 600, USA).
The relative standard deviation was less than 5% for
reproducibility test. The quality assurance was routinely
carried out by using Standard Reference Materials produced
by National Research Center for Certifed Reference Materials,
1368 Ge et al., Aerosol and Air Quality Research, 16: 1366–1377, 2016
China. Precision of quality of ionic measurement data was
checked by anion-cation balance and by comparison of
measured and calculated conductivities. The conductivity
was calculated by the ionic concentration based on the
following equation:
ECcalc (  S cm1 )  {349.7  10(6  pH )  80.0  2[ SO4 2  ]
71.5[ NO3 ]  76.3[Cl  ]  73.5[ NH 4  ]  50.1[ Na  ]
73.5[ K  ]  59.8  2[Ca 2  ]  53.3  2[ Mg 2  ]} /1000
Based on regression and correlation analyses of
calculated and measured conductivities (Fig. S1), the slope
of the regression line was 1.09 for Dandong and 0.99 for
Dalian, while the coefficient of determination was 0.97 and
0.94 respectively. In Dalian, the ratio of calculated vs.
measured conductivity was > 1, suggesting that the ions
was deficient in observation. Simultaneously, the ratio of
total cations to anions was slightly higher than 1 (1.05 as
shown in Fig. S2(a)), revealing anion deficiency in the city,
in agreement with previous literatures. This might due to
some unmeasured anions such as short chain organic acids
(Hontoria et al., 2003; Yang et al., 2012). Overall, the ion
and conductivity balance in both Dalian and Dandong cities
seemed to be reliable according to the acceptable range by
US EPA (Table S1), although the organic anions were absent.
Model Descriptions
A three-dimensional regional Eulerian chemical transport
model, the Nested Air Quality Prediction Modeling System
(NAQPMS) develped by Wang et al.(2000), is utilized in
this study. The new version with the cloud and aqueous
chemistry precess module, which is more suitable for
simulation of wet deposition of acidifying substances in
East Asia, is updated by Ge et al. (2014). The NAQPMS
30 (a)
25
20
Dalian (%)
15
10
5
0
30 3
(b)
percentage in Dandong (%)
25
20
15
10
5
0
3 4
Fig. 2. Distribution of rainfall pH in Dalian (a) and Dandong (b) in 2007.
 
model domain used in this study contains 6570 × 5370
km2 on a Lambert conformal map projection with 30-km
gird resolution horizontally and 20 terrain-following layers
vertically (Fig. S3). The meteorological conditions are
driven by WRF-ARW3.2 and the emission as well as more
details about the model set up is same as Ge et al. (2014).
RESULTS AND DISCUSSION
(1)
Analysis of Precipitation Acidity over Dalian and
Dandong
The distribution of precipitation acidity frequency in Dalian
and Dandong is displayed in Fig. 2. The precipitation acidity
is non-averaged distribution in Dalian. Lower pH values
(4–5) of precipitation at HSJ occurred more frequently than
those at the other two sites. The VWA pH (4.5) for LS is
similar with that at HSJ, with about half of the total samples
belonged to acid rain (based on the definition of pH lower
than 5.6), which is higher than GJZ (7 percent) but lower
than HSJ (69 percent). The rainfall in GJZ was particularly
alkaline, probably due to the high concentration of alkaline-
aerosol such as alkaline calcium and magnesium compounds
emitted from anthropogenic activity, although the sulfate
and nitrate concentration in precipitation are also high
compared to the other two sites in Dalian. In Dandong, the
distribution of rainwater acidity frequency seemed to be in
the same level both at LT and JCZ with high frequency of
low pH (4–6) and more than 50% lowest pH (< 4.5),
indicating heavy acid rain over the city. Table 1 shows the
statistical results of the raining water acidity analysis in
Dalian and Dandong in 2007. Basically, more than 78%
rainfall events were acidic in Dandong with no major
discrepancy between LT and JCZ and close to the annual
volume weight averaged pH (pHvwa). In Dalian, monitored
acid rain frequency was 68% at HSJ station, 46% at LS, and
LS HSJ GJZ
4 5 6 7
LT JCZ
5 6 7
pH
 Ge et al., Aerosol and Air Quality Research, 16: 1366–1377, 2016  1369
Table 1. Overview of the rainfall samples in Dandong and Dalian during 2007.
City Sites Rainfall events Num of Acid rain* Frequency (%)
LT 33 26
Dandong
JCZ 32 25
HSJ 32 22
Dalian LS 24 11
GJZ 14 1 7
* more than 50% samples with pH < 5.6 in an event of rainfall are defined as acid rain.
only 7% at GJZ, respectively. In comparison with Dandong,
the acid rain was obviously less pronounced in Dalian city
with relatively higher yearly pHvwa at HJS, LS (4.5) and
GJZ (5.15). However, the acid rain in both cities seemed to
be at the similar levels as those observed in Southwestern
China (pH are in the range of 4.1–4.6) and Yangzi River
(pHvwa4.5) by (Aas et al., 2007) and (Huang et al., 2008),
and more critical than the acidification process observed in
Beijing (5 years rainfall records with pHvwa = 6.2) reported
by Yang et al. (2012).
Chemistry of Precipitation in Dandong and Dalian
Monthly Volume-Weighted Average of Ion Concentration
Calculated monthly averaged ion concentrations are
presented in Fig. 3. The ion concentrations in rainfall showed
significant seasonal variation with high values in winter
and spring and weak in summer in both Dandong and Dalian.
These ions were found to be correlated to the volume of
precipitation and high concentrations of air pollutants (SO2,
NOx, etc.), as well as the potentially affecting sources and
dominate airflows, such as the anthropogenic heating periods
in autumn and wintertime and the mineral dust emissions
occurring in springtime reported by (Huang et al., 2008).
For instance, high level of SO2 and NO2 concentration in
winter and low in summer provide the coordinated precursors
of the ions in precipitation both in Dandong and Dalian
(Fig. S4). Note that, the highest volume of precipitation
occurred in August and July, with a discrepancy factor of
2. By assuming that the rainfall in July was sufficient to wash
out the air pollutants in a relatively weak local emission
area like Dandong, the ion concentrations in water could be
determined by the volume of rainfall and this might derive
the total ion concentration of August at JCZ (170 µeq L–1)
and LT (136 µeq L–1). However, the theoretical values (or
calculated values) of total ion concentrations of August were
lower than those measured (186 µeq L–1 and 281 µeq L–1 at
JCZ and LT, respectively). Consequently, the air pollutants
would not be cleaned out by wet deposition even under the
high volume of precipitation (> 100 mm) in Dandong. In
Dalian, high volume of rainfall was associated with high
ionic concentrations, highlighting the complexity of wet
scavenging in Dalian. The findings reveal a typical physico-
chemical condition over Northeast China with probably
constant strong influence of regional transport over Dandong
and Dalian, particularly in summer (Huang et al., 2008; Zhang
et al., 2008). Actually, in Northeast China, a persistent
subtropical high-pressure system situated over the western
Pacific, leads to gentle winds favourable for pollutants
stagnation and distribution after an important chemical
Range of pH pHVWA
78.8 3.24–6.69 4.15
78.1 3.17–7.29 4.27
68.8 3.73–7.48 4.51
46 3.45–7.83 4.5
3.98–7.71 5.15
transport controlled by the summer monsoon (Seto et al.,
2002; Gao et al., 2005; Wang et al., 2008). On the other hand,
the regional warm summertime weather and the growth of the
well-mixed boundary layer in that period, act as important
triggers of strong photochemical conversion of SO2 and
NOx resulting in high acidic species concentrations (Gao et
al., 2005). The variation of planetary boundary layer height
(PBLH) is found to play an important role in the stagnation
of anthropogenic pollutants concentrations in summer over
Northeast China (Wang et al., 2008). The convergence of
these physical and chemical reactions undoubtedly towards
an accumulation of the chemical components in precipitation
over Dandong and Dalian even under high wet scavenge
process.
Acidification Process and Neutralization Effect
Among the anions, nssSO42– and NO3– were the major
species with the yearly volume-weighted averaged
concentrations of 71% and 80% of the total anions in Dalian
and Dandong, respectively. Usually, the ratio of nssSO42–
to NO3– (nssS/N) is considered as an indicator of the
acidification status (Wang and Wang, 1996; Fujita et al.,
2000; Tanner, 1999). In 2007, this ratio varied seasonally with
13.1 in winter-spring and 1.05 in summer-autumn over
Dandong (Fig. 4). The dominance of sulfur in acidification
process was thus more pronounced in winter-spring than
that in summer-autumn. The increasing long heating period in
winter, potential source of abundant sulfur emissions, might
not be significantly balanced by NOx emissions essentially
from regional mobile traffic. Over Dalian, the yearly ratio
was 2.35 with high concentrations of both nssSO42– and
NO3– in winter, which is similar with that in Beijing with
the value of 2.7 based on the five-year measurements reported
by Yang et al. (2012). This reflects the strong impact of
local NOx emissions over Dalian where the mobile traffic
is actually much more intense than that in Dandong.
Due to the presence of NH3 and CaCO3, the neutralization
of the acids such as H2SO4, HNO3 and organic acids in
precipitation occurs and the pH of precipitation depends on
the relative abundance of these acids and bases and of the
neutralization reactions amongst them. The neutralization
effects of major bases such as CaCO3 and NH3 was analyzed
by the linear regression model using SO42– and NO3– as
dependent variables and Ca2+ and NH4+ as independent
variables (Migliavacca et al., 2005). Table 2 shows the results
of the regression coefficient. In Dandong, approximately
69.1% of SO42– (64.5% for (NH4)2SO4 and only 4.6% for
CaSO4) could be explained by the two independent variables
used in the regression analysis. Similarly, 60.8% NO3– could
1370 Ge et al., Aerosol and Air Quality Research, 16: 1366–1377, 2016 

Fig. 3. Monthly averaged ion concentrations and monthly precipitation over measurement sites in 2007.

Fig. 4. The ratio SO42–/NO3– in the precipitation in Dalian (a) and Dandong (b); red and black circles in (b) are in summer-
autumn and winter-spring respectively.

Table 2. Fractions of SO42– and NO3– explained by Ca2+ and NH4+ in samples of Dandong and Dalian.
% explained by Ca2+ % explained by NH4+ Total explained (%)
Dandong
SO42– 4.6 64.5 69.1
NO3– –33.1 60.8 22.7
Dalian
SO42– 81.2 16.3 97.5
NO3– 56.4 31.5 87.9

be explained by NH4+. However, no correlation existed
between NO3– and Ca2+. In short, the neutralization of
precipitation acidity over Dandong was mainly due to existing
NH3 probably emitted from agricultural farms and fertilizer
production units. In contrast, the acid neutralization over
Dalian was mainly governed by CaCO3 (large contribution
of CaSO4 (81.2%) and Ca(NO3)2 (56.4%)) emitted from
industrial and construction activities. The difference between
Dandong and Dalian could be attributed to the different
atmospheric chemistry fields: potentially affecting sources,
 Ge et al., Aerosol and Air Quality Research, 16: 1366–1377, 2016  1371

airflow, precipitation phenomena and topography. Following
section will discuss the potential sources of the precipitation
chemistry in these two cities.
SOURCES OF IONS IN RAIN WATER
Source Identification by Factor Analysis
In order to quantify the influence of anthropogenic and
natural sources on the chemistry of the precipitation over
Dandong and Dalian cities, the principal components analysis
(PCA) with mathematical methods, applied worldwide
(Lee et al., 2000; Seto et al., 2000; Migliavacca et al., 2005;
Huang et al., 2008), has been deployed in this study using
SPSS software (version 15.0). The Varimax Rotation was
applied to the data set for simplifying the expression of the
principal components (PC). Results are presented in Table 3.
In Dalian, two factors explained 72% of total variance versus
four factors in Dandong for 85% of the total variance. In
Dalian, the first factor (F1), with a variation of 40% of the
raw data, showed high loading for pH, Cl–, Na+, K+, Ca2+
and Mg2+, reflecting natural sources. Basically, Cl–, Na+
and K+ characterized the contribution of sea salts (Seto et
al., 2000; Huang et al., 2008), while Ca2+ and Mg2+ were
probably from dust. The second factor (F2), explaining 32%
of the total variation, showed high loading for SO42–, NO3–,
NH4+ and K+. This factor characterized the anthropogenic
sources, of which SO42–, NO3– and NH4+ derived from coal
burning, mobile emissions, farming activities and human/
animal excrement. The high loading for K+ associated with
NH4+ in F2, could be considered as a signal of biomass
burning (Migliavacca et al., 2005). On the other hand, the
pH seemed to be mainly associated with Ca2+ and Mg2+.
Therefore, the anthropogenic emissions, sea salts and dust
were the main sources of rainwater ions in Dalian. In
Dandong, F1 explained 29% of the total variation with high
loading for F–, Ca2+ and Mg2+ mainly emitted from dust.
The second factor F2 (23%) represented sea salt sources
with high loading for Cl–, Na+ and K+. With the total
variance (F1 + F2) of 52%, the contribution of natural
sources to rainwater ions was found to be more significant
in Dandong than that in Dalian. F3 showed higher loading
for SO42–, NO3– and NH4+ characterizing anthropogenic
emissions, with 20% of the total variance. F4 (13% of the
total variance) highlighted good correlation among pH, SO42–
(–0.5) and NH4+ (0.24). Therefore, the pH of the precipitation
over Dandong was more influenced by (NH4)2SO4 than
CaCO3.
Source Identification by Backward Trajectory Analysis
The backward trajectory analysis had been widely used
in studying the influence of the rainout and washout processes
(Okita et al., 1996; Bertrand et al., 2008; Huang et al.,
2008; Yamagata et al., 2009; Zhou et al., 2009; Izquierdo
et al., 2012; Shi ChunE, 2014). In this study, the 72-h back
trajectories were calculated for four time sequences (00:00,
06:00, 12:00 and 18:00 UTC) per day (rainy day) at 100 m
altitude, and clustered using the clustering tool of
HYSPLIT4.8 (Fig. 5). All rainwater samples were collected
and associated with concurrent values of the trajectories
and grouped on the basis of their intraday prevailing wind
directions. In both Dalian and Dandong cities, four main
transport patterns have been dissociated such as local sector
with the wind speed lower than 2 m s–1 and air masses from
all directions around the sites, W–N–NW sector, E sector, and
S–SE sector (Table 4). In Dalian, the local sector (mostly
occurring in summer) contributed to about 51% of the total
air-mass with dominance of Ca2+ and Mg2+ concentrations.
The W–N–NW sector (14% of the total air-mass) consisting
of air masses mainly from Siberia area in spring and autumn,
governed the impacts of dust with the highest concentrations
of Ca2+ (148.6 µeq L–1) and Mg2+ (45.6 µeq L–1). The third
sector generated from the east including Korea peninsula
(21% of the total air-mass, mostly occurring in spring and
summer) was dominated by SO 4 2– , NO 3 – and NH 4 +
concentrations, slightly higher than local sector loadings.
The pH value of E sector was the lowest in all four sectors,
corresponding to the lowest cation concentrations as well
(24.5 µeq L –1 and 13.2 µeq L –1 for Ca 2+ and Mg 2+ ,
respectively). The S–SE sector (14% of the total air mass,
from the Pacific and Yelow sea with crossing over Shandong
Province) showed the highest concentrations of anthropogenic
ions (210.7 µeq L–1 for SO42–, 76.6 µeq L–1 for NO3– and 103.5

Table 3. Principle component analysis of the major ions.

Dalian Dandong
Variable
F1 F2 F1 F2 F3 F4
pH 0.71 –0.28 –0.01 –0.01 0.10 0.96
F– 0.49 0.48 0.87 0.17 0.14 –0.04
Cl– 0.86 0.24 0.46 0.80 –0.08 0.03
SO42– 0.44 0.80 0.36 0.33 0.58 –0.50
NO3– 0.21 0.84 –0.07 0.01 0.94 –0.02
Na+ 0.87 0.26 0.35 0.75 0.13 –0.15
NH4+ –0.05 0.78 0.39 0.11 0.82 0.24
K+ 0.68 0.68 –0.09 0.92 0.13 0.01
Ca2+ 0.74 0.40 0.82 0.35 0.05 0.05
Mg2+ 0.73 0.46 0.89 0.02 0.12 –0.12
Variance (%) 40 32 29 23 20 13
Category Sea salt/Dust Anthropogenic Dust Sea salt Anthropogenic
Note: bold data (PCs > 0.5) are considered significant.
1372 Ge et al., Aerosol and Air Quality Research, 16: 1366–1377, 2016 

Fig. 5. Mean 72 hours backward trajectory clusters in rainfall days in Dalian (a) and Dandong (b) in 2007.

Table 4. Volume-weighted mean concentrations (µeq L–1) of major ions from different air mass clusters in Dalian and
Dandong.
Sector No. Rain (mm) pH SO42– NO3– F– Cl– NH4+ Ca2+ Mg2+ Na+ K+
Dalian
Local 8 191.2 4.25 95.2 31.3 9 9 17.3 82 33.8 17.2 15.9
W–N–NW 4 124.4 4.48 200.4 38.2 17.4 146.6 133.2 148.6 45.6 96 11.4
E 5 68.5 4.13 116.6 43.1 11.4 36.3 55.2 24.5 13.2 15.8 3.6
S–SE 4 82.1 4.5 210.7 76.6 11.1 65.9 103.5 78.3 26.3 38.8 8
Dandong
W–N–NW 5 132.7 4.3 428.4 47.8 20 28 118.1 241.2 82.6 66.7 41
Local 12 333 4 174.5 58.4 30.5 25.2 57.3 167.9 45.8 32.2 6.8
E 5 178.4 4.2 304.3 46.3 14.1 13.3 85.9 100.3 46.8 31.1 22.5
S–SE 6 262.5 4.25 61.6 19.8 5.7 24.6 12.9 71 23.6 43.3 1.9
No.: The number of rain samples in each sector.

µeq L–1 for NH4+) as well as relatively high concentrations
of sea-salt ions (65.9 µeq L–1 for Cl– and 33.8 µeq L–1 for
Na+). This highlights the contribution from the Pacific and
Shandong Province to air pollution over Dalian. In Dandong,
the local sector (44% of the total air mass) showed the
lowest rainwater pH value with high level concentration of
SO42–, NO3– and low NH4+. The contribution of W–N–NW
sector mostly occurring in winter and spring (dust influence)
remained same as that in Dalian. It is worthy to note that, the
high concentration of F– (30.5 and 20 µeq L–1) is loading in
local and W–N–NW sector, which is much more higher than
that in Dalian (with highest concentration of 17.4 µeq L–1
in W–N–NW sector) although the latter is more affected by
the industrial emissions. As we known, the F– in the
precipitation is mainly originated from the anthropogenic
emission such as coal burning, as well as the natural emissions
like the volcanic eruption and the sea salt (Friend, 1989;
Saether et al., 1995; Walna et al., 2013). Our findings imply
the fluoride in North China as Dandong and Dalian is
mainly controlled by the natural emissions instead of the
anthropogenic emissions. However, Dandong was particularly
influenced by high concentrations of SO42– (304.3 µeq L–1)
in E sector (in autumn) and low value in S-SE sector (in
summer, 61.6 µeq L–1). This reveals strong impact of trans-
boundary pollution from Korea peninsula on Dandong.
Source Identification by NAQPMS
The source tracing method coupled in NAQPMS has
usually been used for O3 and PM10 source-receptor
relationship analysis (Li et al., 2008; Wu et al., 2011), and
also been investigated the sources of acidity substances
deposition in East Asia by Ge et al.(2014). Based on the
same method as that in Ge et al.(2014), the source of sulfur
and nitrogen in wet deposition in Liaoning has been studied.
 Ge et al., Aerosol and Air Quality Research, 16: 1366–1377, 2016  1373

Utillizing Geographical Information System (ArcGIS), the
simulated region are devided into seven areas including:
Liaoning, Northeastern China (NEC) except Liaoning, North
China Plane (NCP), West China (WC), East China (EC),
Southeast China (SEC), Central China (CC) and Outboard
(Fig. S3).
The simulated yearly total wet deposition of sulfur (S),
nitrogen from NO3– (N–NO3–) and nitrogen from NH4+ (N–
NH4+) in Liaoning are 1.29 × 105 t × S, 4.55 × 104 t × N and
5.25 × 104 t × N, respectively (Table 5). Among the total
wet deposition in Liaoning, almost 47% of S and 38% (83%)
of N–NO3– (N–NH4+) are from local emission. It should be
noted that wet deposition of acidify substances from regional
transported are significant, with NCP, EC and Outboard as
the three largest imported areas. Fig. 6 shows monthly
distributions and the contributions of the S, N–NO3– and
N–NH4+ wet deposition from eight areas. The largest amount
appears in summer with large contribution from Outboard
(e.g., Korea and Japan) and EC (e.g., Shangdongv Province),
which is consistent with the resluts of the Backward
Trajectory Analysis. The largest local contribution to the
N–NH4+ wet deposition among the three species suggested
the significant impacts of the local agriculture acivities.

Table 5. The wet deposition, and the contribution of S and N in Liaoning from different area simulated by NAQPMS (Unit:
× 103 t S (N) × yr–1).
Total NEC Liaoning NCP EC Outboard SEC WC CC
129.16 4.07 60.99 14.75 18.32 29.66 0.07 0.36 0.82
S
% 3.2 47.2 11.4 14.2 23.0 0.1 0.3 0.6
– 45.48 2.37 17.30 5.20 9.62 10.18 0.06 0.16 0.58
N–NO3
% 5.2 38.0 11.4 21.1 22.4 0.1 0.4 1.3
52.51 0.53 43.81 2.18 2.20 3.74 0.00 0.01 0.04
N–NH3
% 1.0 83.4 4.2 4.2 7.1 0.0 0.0 0.1

Fig. 6. Simulated Source identification of S and N wet deposition volume in (a) and percentage in (b) by NAQPMS.
1374 Ge et al., Aerosol and Air Quality Research, 16: 1366–1377, 2016 

Influence of Washout and Rainout
Sequential sampling has been carried out in summer in
Dandong (at rural site) and Dalian (HSJ & GJZ) to thoroughly
evaluate the contribution of long range transport in cloud
(rainout) and washout process below-cloud. Fig. 7 shows
the averaged concentrations of chemical species of collected
fractions. In both Dandong and Dalian, the chemical contents
decreased through the precipitation increment. This might
be due to scavenging of air pollutants under the cloud into
the rainfalls in the first fractions. Based on the method
employed by Aikawa and Hiraki (2009, 2014) to evaluate
the washout and rainout contributions (with the assumption
that the chemical ions in later precipitation increment would
be attributed to scavenging process through the rainout
mechanism), we have estimated the washout and rainout
contributions for Dandong and Dalian as prsented in Table 6.
Both the rainout and the washout mechanisms accounted
for about 50% of the total SO42– deposition in Dandong over
rural site. This supports various trends recently published
worldwide for rural sites such as 47–53% in France (Bertrand
et al., 2008) and 51–49% in Japan (Aikawa et al., 2014). In
urban and suburban sites like GJZ and HJS, the conrtibution
of the rainout has decreased to 12 % and 35%, similar with
that found in Beijing (Liu and Huang, 1993) but lower than
that reported in Japan by Aikiwa (2009, 2014) and Brazil
by Migliavacca (2010). This might be due to the fact that
coarse sulfate particles below-cloud in the urban cities of
northern China are more efficiently scavenged by raindrops
than fine particles (Samara and Tsitouridou, 2000). Such
explanation is undoubdetely confirmed by resulting high

800
at DD (µeq/l)

400

0
1# 2# 3# 4# 5# 6# 7#
2000
2- - - -
SO4 NO3 F Cl
at GJZ (µeq/l)

1500 + 2+ 2+ +
NH4 Ca Mg Na
+
1000 K

500

0
1000 1# 2# 3# 4# 5# 6# 7#
at HSJ (µeq/l)

500

0
1# 2# 3# 4# 5# 6# 7#
Fraction
Fig. 7. Evolution of the chemical content through the rainfall Fraction.

Table 6. The contributions of mainly ions by rainout/washout process (%).

SO42– NO3– NH4+ Ca2+
Location * ** Characteristics Reference
R W R* W** R* W** R W***

Dandong, China 44 56 50 50 54 46 34 66 Rural This study

HSJ, China 35 65 30 70 25 75 22 78 Suburban This study
GJZ, China 12 88 8 92 16 84 12 88 Urban This study
Chongqing, China 53 47 26 74 22 78 Urban (Liu and Huang, 1993)
Beijing, China 35 65 26 74 12 88 Urban (Liu and Huang, 1993)
Coastal Japan 25 75 (Kitada et al., 1993)
Opme, France 47(28–76) 53 Rural (Bertrand et al., 2008)
Porto Alegre, Brazil 70–90 10–30 Urban (Migliavacca et al., 2010)
Kobe, Japan 84 16 26 74 Urban (Aikawa et al., 2014)
44 56 40 60 (Aikawa et al., 2014)
Toyo-oka, Japan Suburban
45 55 34 66 (Aikawa and Hiraki, 2009)
Tamba, Japan 51 49 35 65 Rural (Aikawa et al., 2014)
Note: *Presented Rainout, **Presented Washout.
 Ge et al., Aerosol and Air Quality Research, 16: 1366–1377, 2016  1375
contributions of Ca2+ through washout mechanism at all
three sites (66%, 78% and 88%), since Ca2+ exists only in
coarse state. The nitrate deposition in Dandong also showed
the fifty-to-fifty percent contribution between the the rainout
and the washout process in contrast to the strong washout
contriburion found in Dalian at HSJ (70%) and GJZ (92%).
Many of previous studies reported about one-thrid to two-thrid
contributions to rainout and washout over rural and urban
areas (Kitada et al., 1993; Liu and Huang, 1993; Aikawa and
Hiraki, 2009; 2014). In comparison with this study, it is
obvious to note that the washout scaveging below-cloud in
Dalian (GJZ) under high local emissions, is more significant
than that in Dandong with relatively minor local emissions.
CONCLUSION
The measurement analysis performed in this study shows
the evidence of acid rain over Dandong and Dalian cities in
2007 (with strong yearly averaged pHvwa) and provides
insights into the mechanisms behind such phenomenon. Based
on rainwater volume weighted calculation, factor analysis
(with the approach of principal component), backward
trajectory description (based on HYSPLIT4), source-tracing
simulation and rainout/washout mechanism analysis, this
paper had identified various and complex physico-chemical
processes such as pollutant accumulation and stagnation
over both cities even under high wet scavenge particularly
in summer (due to the growth of the well-mixed boundary
layer with regional warn weather favourable to strong
photochemical conversion of SO2 and NOx), long range
transport with rainout scavenging in-cloud, and constant
seasonal influence of regional air masses on acidification
process, as the most plausible triggers of acid rain diffusion
over Dandong and Dalian.
In summary, the present findings recommend that an
effective acid rain control program over Liaoning should
be rigorously conceived at both local and regional scales. In
terms of direct environmental implication, regional approach
of environmental impact assessment with integration of the
trans-boundary pollution should be developed in China.
Much effort should be made for regional emission reduction,
particularly in the potential polluting surrounding areas of
Liaoning Province. Enhanced collaboration with neighboring
countries within EANET network might be beneficial. In
the further study, associated impacts of the acid rain on
local ecosystems, agriculture, soil and aquatic systems in
Northeastern China will be investigated. Facing the increasing
of the acid precursor’s emission, strict strategies with rigorous
environmental constraints are necessary to effectively reduce
the environmental burden.
ACKNOWLEDGEMENT
This work was supported by the National Natural
Science Foundation of China (41305113, 41575123), and
the Strategic Priority Research Program (B) of the Chinese
Academy of Sciences (Grant No. XDB05030200), the
National Science and Technology Support Program (grant
2014BAC22B04). We thank The Liaoning Environmental
Monitoring & Experiment Center for collecting the rainfall
samples and carrying out the measurements.
SUPPLEMENTARY MATERIALS
Supplementary data associated with this article can be
found in the online version at http://www.aaqr.org.
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