Environ Earth Sci (2016) 75:209
DOI 10.1007/s12665-015-4997-z
ORIGINAL ARTICLE
Chemical composition and source identification of rainwater
constituents at an urban site in Xi’an
Jun Xiao1
Received: 12 June 2015 / Accepted: 28 September 2015 / Published online: 25 January 2016
Ó Springer-Verlag Berlin Heidelberg 2015
Abstract Major ions, pH and electric conductivity (EC)
in rainwater samples collected from June 2011 to July 2012
were analyzed to evaluate chemical characteristics and
source apportionment of rainwater in Xi’an, a city located
on the loess deposits. The rainwater was slightly alkaline
with a daily volume-weighted mean (VWM) pH of 7.7,
which ranged from 7.4 to 8.4. The VWM concentrations of
major ions followed the order of Ca2? [ SO42- [
NH4? [ NO3- [ Cl- [ Na? [ K? [ Mg2? [ F-. Ca2?
and SO42- dominated in cations and anions, respectively.
Investigations of neutralization factors indicated that the
acidity of rainwater in Xi’an was neutralized by NH4? and
Ca2?, which presented relatively higher neutralization
capability than cities in southern China. The back trajec-
tory analysis showed that the chemistry of rainwater in
Xi’an is influenced by local pollutions sources and soil dust
in local and remote area. Large inputs of soil dust and coal
combustion during the winter and spring led to higher
values of major ions and pH values during dry seasons than
wet seasons. The principal factor analysis, correlation
analysis, and source apportionment indicated that SO42-
and NO3- were from anthropogenic sources, while Ca2?,
K?, and Mg2? were from crust fractions. The estimated
annual wet depositions for sulfur, nitrogen, and calcium
were 3.9, 1.5, and 4.2 t/km2, respectively. Although rain-
water acidity in Xi’an was mainly caused by H2SO4, the
contribution of HNO3 will be enhanced due to increasing
NOx and relatively stable SO2 emissions in the future. The
& Jun Xiao
xiaojun@ieecas.cn
1 acid area in the world after Europe and North America
State Key Laboratory of Loess and Quaternary Geology,
Institute of Earth Environment, Chinese Academy of
Sciences, Xi’an 710061, China
high concentrations of EC, SO42-, and NO3- in rainwater
indicated Xi’an is severely polluted. To improve air quality
in Xi’an, simultaneous reduction of particle emissions and
fossil fuel and vehicles emissions are worthy of advocating.
The results have implications for identification of potential
sources in rainwater and for evaluation of air quality
improvement in Xi’an and other similar cities in China.
Keywords Rainwater  Chemical composition  Source
apportionment  Neutralization factor  Anthropogenic
source
Introduction
The rainwater composition is strongly affected by chemical
composition of the atmosphere and plays an important role
in scavenging soluble components from the atmosphere
(Al-Khashman 2005; Liu et al. 2013; Chidambaram et al.
2014; Li et al. 2015). Therefore, rainwater chemistry is a
useful index of chemical composition of the atmosphere
and helps us to understand the relative contributions of
different sources of atmospheric pollutants (Zhang et al.
2012a, b; Niu et al. 2014; Rao et al. 2015). The issue of
acid rain, which was caused by increased emissions of SO2
and NOx, has received more and more attention on global
scale for the last several decades because of its notable di-
rect adverse effects on ecosystem and indirect effects on
human health (Hu et al. 2003). Since the 1970s, rapid
economic growth and increased energy demand have
resulted in severe air pollution problems throughout China
(Larssen and Carmichael 2000). China is the third main
(Larssen et al. 2006; Xu et al. 2015). According to the
Ministry of Environmental Protection of the People’s
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Republic of China (2014), the acid rain area accounted for
about 10.6 % of China’s land area, which is mainly dis-
tributed along the Yangtze River and south of its middle
and lower reaches. The chemical composition of rainwater
has been widely investigated in China, especially in
southern China (Larssen et al. 2006; Huang et al. 2008;
Cao et al. 2009; Han et al. 2010; Wang and Han 2011; Wu
et al. 2012; Xiao et al. 2013; Niu et al. 2014; Yu et al.
2015). Their results indicated that the rainwater composi-
tion was highly influenced by fossil fuel combustion and
natural soil dust. Although the concentrations of acidic
species SO42- and NO3- in northern China are much
higher than that in southern China, the severe acid rain
mainly occurred in southern China, probably reflecting
different formation mechanisms of acid rains in different
areas (Huang et al. 2009). Thus, there exists an urgent
requirement for a more detailed understanding of acid rain
in various regions of China, especially in northwestern
China.
Xi’an, the capital of Shaanxi Province and the largest
city in northwestern China, is located on the Guanzhong
Plain on the southern edge of the Loess Plateau. It is also a
famous tourism city in northwestern China and a center for
politics, economy and culture. With fast urbanization and
industrialization, Xi’an is subject to extensive and serious
air pollution in recent years (Cao et al. 2005; Zhang et al.
2011). Lu et al. (2011) showed chemical characteristics of
spring rainwater in Xi’an. Bai and Wang (2014) studied
anthropogenic influence on rainwater in Xi’an by sulfur
isotope and trace elements analyses. However, up to date,
systematic studies on the rainwater chemistry in Xi’an
were few.
To fill the knowledge gaps on rainwater chemistry in
Xi’an, pH, EC, and main ions in rainwater were analyzed
based on 32 continuous rainwater samples collected from
Jun. 20, 2011 to Jul. 8, 2012. The aims of this study are to:
(1) gain a deep understanding of rainwater characteristics;
(2) identify the sources of main ions in rainwater; and (3)
evaluate air quality in Xi’an. This study will provide useful
information for identification of potential sources in rain-
water and improvement of air quality in Xi’an and other
similar cities in China.
Methods
Study area
Xi’an (33°390 N–34°440 N, 107°400 E–109°490 E) is bounded
by Qinling Mountain on the south and east, and by Loess
Plateau on the north. Xi’an has a typical temperate conti-
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Environ Earth Sci (2016) 75:209
nental semi-humid climate, with annual average atmo-
spheric temperature and rainfall of 13–15 °C and
500–700 mm, respectively. The main precipitations are in
the rainy season from July to September every year. Cloud
water originates from Pacific air masses in summer while
Siberian and Mongolian air masses prevail in winter (Bai
and Wang 2014). The predominant wind direction in winter
and autumn is northeast, while in summer and spring is
southwest. Coal is used extensively, especially in winter
and spring for heating. The sampling site was located in
Yuanqizhai Village at west south of Xi’an, which is about
2.5 km away from the bypass highway (Fig. 1).
Sampling and analytical procedure
The sampler was placed on the roof of a building about
10 m high from ground level in an office building. Rain-
water samples were collected manually from start of each
rain event with a funnel sampler that was located approx-
imately 1.5 m above the roof. Prior to use, the sampler was
cleaned with acid (2 N HCl) and soaked in with Milli-Q
water (18.2 MX cm), then finally rinsed with Milli-Q water
and dried. Between two rain events, the sampler was
covered with a clean large polyethylene sheet to avoid
being polluted by dry deposition. A total of 32 samples
were collected.
The electric conductivity (EC) and pH were determined
in situ using portable Orion EC/pH meter at the end of the
rain events. Immediately after collection, rainwater sam-
ples were in situ filtered on collection through 0.22 lm
WhatmanÒ nylon filters to remove the insoluble particles.
A 60-mL aliquot was stored in a pre-cleaned high-density
polyethylene (HDPE) bottle and acidified to pH \ 2 with
6 M ultrapure HNO3 for cation analysis. A 30-mL aliquot
of the un-acidified sample was collected for anion analysis.
Then, bottles were wrapped with a parafilm strip around the
closure to ensure no leakage. All of the samples were
stored at 4 °C until analysis. Water samples were analyzed
for Ca2?, K?, Mg2?, and Na? by a Leeman Labs Profile
ICP-OES at Nanjing Institute of Geography and Limnol-
ogy, Chinese Academy of Sciences. Repeated analyses
demonstrated reproducibility within 2 %. NH4? concen-
trations were determined by spectrophotometry using the
Nessler method. A Dionex-600 ion chromatograph was
used for F-, Cl-, NO3-, and SO42- analysis at the Institute
of Earth Environment, Chinese Academy of Sciences. The
average replicated sample reproducibility was 0.5–1 %
(2r). The volume-weighted mean (VWM) was used to
calculate the concentrations of ions, so as to account for the
effect of precipitation amount on ion concentrations
(Staelens et al. 2005).
Environ Earth Sci (2016) 75:209 Page 3 of 12 209

Fig. 1 Map of Xi’an city

showing the location of
sampling site

Results and discussion
pH and ionic composition
Statistics of the composition of major ions, pH, EC, and
VWM in rainwater are presented in Table 1. The
equivalence ratio of the sum of anions to that of cations
(Ranions/Rcations) is usually regarded as an indicator of the
completeness of measured major constituents (Wang and
Han 2011). The Ranions/Rcations ratio was 0.7 in this
study, suggesting that some anionic species were miss-
ing. Since the soil and sands in the arid and semi-arid
regions of northern China are calcareous and alkaline,
the observed anion deficiency is most likely due to the
exclusion of HCO3- and CO32- from the measurements
(Xu et al. 2009). The values of arithmetic mean are
higher than those of median (Table 1), indicating that the
frequency distributions are asymmetric and skewed by
those high concentration values. The VWM is smaller
than arithmetic means, indicating that the higher con-
centrations are usually associated with lower precipita-
tions (Table 1).
The rainwater samples were slightly alkaline with daily
pH ranged from 7.4 to 8.4, with a VWM value of 7.7
(Table 1). Natural rainwater in a clean atmosphere is
generally considered to be weakly acidic. All the rainwater
samples in Xi’an had pH [ 5.6, suggesting acid rain events
in this area were not serious and there are possible inputs of
alkaline species into rainwater (Larssen and Carmichael
2000). No obvious correlations between pH value and
SO42- and NO3- (Table 2) indicated that most of the
SO42- and NO3- are present as salts (NH4NO3, CaSO4)
rather than HNO3 and H2SO4. Positive correlations are
obtained between NH4? and SO42- and NO3- (Table 2),
indicating that NH3 will first react with H2SO4 and then the
remaining NH3 will be taken up by HNO3.

Table 1 Volume-weighted mean (VWM) concentrations of ions (in leq/L), electrical conductivity (EC) (in lS/cm) and pH (in unit) along with
statistical results in rainwater samples of Xi’an
Component pH EC K? Na? Ca2? Mg2? NH4? F- Cl- NO3- SO42- nssK? nssCa2? nssMg2? nssSO42-

VWM 7.7 128.4 65.0 109.3 478.4 57.9 272.1 28.8 129.9 122.9 446.8 63.6 457.4 44.6 393.2
Mean 7.7 161.5 79.2 101.5 662.5 86.9 363.3 29.9 136.5 162.5 612.3 77.4 633.4 66.9 534.4
Median 7.7 139.0 27.5 56.4 492.9 69.8 264.2 28.9 108.1 112.0 398.8 26.9 471.2 53.7 350.9
SD 0.3 114 95.0 208 606 99.1 354 13.8 98.3 166 627 92.9 579.6 76.3 552.1
Min 7.4 30.3 2.6 4.6 58.8 5.4 29.5 4.2 21.4 8.1 38.5 2.5 56.2 4.2 33.9
Max 8.4 478.0 344.5 962.9 2123 478.8 1334 60.0 432.9 621.0 2378 336.9 2030 368.6 2093
Level of confidence is 95 %
VWM volume-weighted mean, SD standard deviation, Min minimum, Max maximum, nss non-sea salt fraction, nssX X-{[X/Na]sea 9 [Na]}, X is
the concentration of the ion of interest (Budhavant et al. 2011)

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Table 2 Matrix of correlation coefficients of ionic concentrations (in leq/L) in rainwater samples from Xi’an
pH EC K? Na? Ca2? Mg2? NH4? F- Cl- NO3- SO42-

pH 1
EC 0.26 1
K? 0.27 0.77** 1
?
Na 0.33 0.72** 0.86** 1
Ca2? 0.32 0.95** 0.78** 0.68** 1
Mg2? 0.26 0.80** 0.76** 0.64** 0.86** 1
NH4? 0.34 0.95** 0.80** 0.77** 0.97** 0.86** 1
F- 0.79** 0.44* 0.28 0.39* 0.45** 0.44* 0.52** 1
Cl- 0.28 0.63** 0.66** 0.80** 0.61** 0.63** 0.66** 0.39* 1
NO3- 0.27 0.79** 0.71** 0.71** 0.84** 0.83** 0.90** 0.44* 0.58** 1
SO42- 0.34 0.95** 0.79** 0.75** 0.97** 0.84** 0.99** 0.51** 0.65** 0.86** 1
Bold text shows strong correlations
** Correlation is significant at p \ 0.01 level (2-tailed); * Correlation is significant at p \ 0.05 level (2-tailed). Correlation coefficients:
0.60–1.00 = strong correlation; 0.50–0.59 = moderate; 0.40–0.49 = weak; 0.00–0.39 = little or no association

F- K+
a K+
Na+ b 4.0% c nssSO42-
Na+
3.8% 6.4%
NH 4+ 6.6% Cl -
27.7% 11.1% 17.8% 23.0%
Ca 2+
ssSO42-3.1%
28.0%
nssSO42- NO3- NO3- 7.2%
Mg2+ 5.9% 54.0% 16.9%
Cl - 7.6%
Mg2+
Ca 2+ ssSO42- F- NH 4+ 3. 4%
48.7% 7.4% 1.7% 15.9%

Fig. 2 Percent contribution in Xi’an rainwater: a of each cation to total cation; b of each anion to total anion; c of each ion to total ions. Ca2?
and SO42- dominated in the cation and anion, respectively. nssSO42- = non-sea salt fraction of SO42-, ssSO42- = sea salt fraction of SO42-

The VWM concentration showed that the concentrations of
major ions were in the order of Ca2? [ SO42- [ NH4? [
Cl- [ NO3- [ Na? [ K? [ Mg2? [ F- (Fig. 2). The ion
concentrations show higher dispersions around their mean
values according to the standard deviations (SD), which reveal
greater variation in levels of ionic compositions of rainwater.
Ca2? is the most abundant ion among the cations, accounting
for 48.7 % of the total cations. NH4? is the second abundant
cation and contributes 27.7 % of the cations (Fig. 2b). With-
out considering HCO3-, SO42- is the most abundant ion
among the anions, accounting for 61.4 % of the total anions,
among which nssSO42- accounting for 54.0 %. Cl- is the
second abundant anion and contributes 17.8 % of the total
anions (Fig. 2c). Ca2?, NH4?, SO42- and Cl- combined
account for 78 % of the total ions (Fig. 2a). The high SO42-
concentrations were due to the fact that coal was the major fuel
consumption source in China (Zhang et al. 2007). The high
Ca2? concentrations may be from the soil dust in this area
(Cao et al. 2013).
Monthly variations
The monthly VWM concentrations of pH, Ca2?, NH4?
(nssSO42- ? NO3-) and EC in rainwater are shown in
Fig. 3. It can be seen that the pH, Ca2? and EC showed
high values in winter and spring (Fig. 3). As Xi’an is
located on the Loess Plateau, the high Ca2? concentrations
in dry months may be caused by frequent dust events
(abundant in CaCO3) from both the long-range transport
and local fugitive dusts. In addition, the majority of rainfall
in Xi’an takes place in summer and autumn. Soils are
therefore relatively wet and surface dusts are not easily
incorporated into the air, which decrease the concentrations
of Ca2? in summer and autumn. Wu et al. (2013) showed

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Fig. 3 Monthly mean concentrations of pH, Ca2?, NH4?,
(nssSO42-?NO3-) and EC in rainwater. These parameters showed
synchronous change with high values in dry months and low values in
wet months
that dust events can restrain rainwater acidity and increase
pH of rainwater by increasing alkaline materials in atmo-
sphere and rainwater. Thus, the high pH may also be
related to the dust events in dry season. The monthly
average concentrations of (nssSO42- ? NO3-) and NH4?
showed the same variations with pH, Ca2?, and EC. On the
one hand, the dilution of contaminants in rainwater in
summer and autumn will lead to lower ions content than
that in winter and spring as discussed above. On the other
hand, the period from November to the next March belongs
to the warming period in Xi’an, when the coal combustion
was the main source of warmth (Bai and Wang 2014). The
average daily coal consumption in Xi’an is 452 thousand
tons in 2012 (XAMBS 2013). The high quantity of coal
combustion in winter and spring can lead to high concen-
trations of SO2 and NOx in atmosphere in these seasons,
which can be transformed into SO42- and NO3- in rain-
water finally (Al-Khashman 2009; Zhang et al. 2012b; Bai
and Wang 2014). Zhang et al. (2011) also showed that the
major ions in atmospheric aerosols in Xi’an were in the
species of (NH4)2SO4, NH4HSO4 and NH4NO3, and their
concentrations were highest in winter, due to high coal
combustion. Therefore, the high concentrations of
(nssSO42- ? NO3-) in winter and spring would be related
with high coal combustion in these seasons. This was also
supported by the sulfur isotope in rainwater in Xi’an (Bai
and Wang 2014). Moreover, the scavenging of pollutants
from air by rainwater is also an important process affecting
monthly variations of pollution species (Zhang et al.
2012b). Therefore, both of the high emissions in cold
season and the high scavenging of pollutants in warmer
Page 5 of 12 209
season caused this temporal variation of the concentrations
of SO42-, NO3-, and NH4?.
Comparison with other cities
Rainwater chemical compositions can reflect air pollution
levels to some extent. The chemical composition and pH of
rainwater in major cities in China and in the world were
compared to decipher their pollution levels and rainwater
acidity (Table 3). The VWM pH value in Xi’an was quite
close to those in northwest cities, such as Xining (Zhang
et al. 2003a, b) and Lanzhou (Xu et al. 2009), but much
higher than those in southern cities and other sites in the
world (Table 3). Generally, the pH of rainwater in China
showed a distinct geographical variation with relatively
higher pH in northern cities than southern cities. This may
be related with geographical distributions of soil dust,
because northern cities located in arid or semi-arid regions
and subjected to high dust loading and Ca2? in soil dust
neutralized rainwater acidity. Overall, ion concentrations in
rainwater, especially the Ca2?, SO42-, and NO3- in Xi’an
were higher than those in other sites in China and in the
world (Table 3). It is more evident when compared with
the clean sites of Nam Co (Li et al. 2007; Zhang et al.
2012c) and background monitoring site of rainwater
chemistry of Waliguan (Tang et al. 2010). The EC values
ranged from 30.3 to 478 lS/cm, with a VWM of 128.4 lS/
cm. The high EC values and ion concentrations in rain-
water reflected strong mineralization, worse atmosphere
environmental quality, and anthropogenic forces in Xi’an.
Acid neutralization
The rainwater acidity is strongly controlled by concentra-
tions of acid-forming ions, such as SO42- and NO3-, and
the alkaline species, such as Ca2?, NH4? and Mg2?, can
neutralize the acidity. As mentioned above, rainwater in
Xi’an has a high NO3- concentration, and the SO42-
concentration is the highest in China (Table 3). However,
compared with acid rain areas in China, acid rain in Xi’an
is not serious. The strong positive correlations among
SO42-, NO3-, Ca2?, Mg2?, and NH4? (Table 2) indicated
that acidic anions are neutralized by base cations. Leaching
experiments on the dusts collected in northwest China with
deionized water showed that the leaching waters were
alkaline (7.5–8.7), which were similar to the rainwater in
Xi’an (Zhang et al. 2003a). Thus, it is obvious that the
relatively high pH values of rainwater in Xi’an are not due
to lack of acidic ions in rainwater, but rather due to neu-
tralization of acidity by alkaline substances.
The capacity of acidity neutralization of rainwater is
calculated as fractional acidity (FA), i.e., FA = [H?]/
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209 Page 6 of 12 Environ Earth Sci (2016) 75:209

Table 3 Comparison of the major ion concentrations (in leq/L) and pH values (in unit) in Xi’an with other sites in China and worldwide
Site pH EC K? Na? Ca2? Mg2? NH4? Cl- NO3- SO42- References

Xi’an 7.7 128 65.0 109 478 57.9 272.1 129.9 123 447 This study
Xi’an 6.6 82.8 13.8 31.1 426 36.6 229.8 38.7 129 490 Lu et al. (2011)
Xi’an 5.9 120 28.6 40.3 539 66.5 63.0 82.0 741 Bai and Wang (2014)
Xining 7.1 78.2 69.2 96.6 314 37.9 160.6 48.8 48.1 84.0 Zhang et al. (2003a)
Lanzhou 7.7 95.7 7.26 12.3 886 46.5 57.2 27.9 74.4 208 Xu et al. (2009)
Beijing 5.1 76.9 17.7 25.0 607 40.4 185.6 104 109 316 Xu and Han (2009)
Dalian 4.8 55.4 6.9 36.2 78.8 25.3 107.8 59.8 51.4 168 Zhang et al. (2012b)
Nanjing 5.2 12.1 23.0 295 31.7 193.2 143 39.6 242 Tu et al. (2005)
Jinhua 4.5 20.3 5.3 7.5 56.1 4.4 97.0 10.3 37.0 117 Zhang et al. (2007)
Guangzhou 4.5 32.9 55.0 104 17.0 70.6 86.8 53.4 163.3 Cao et al. (2009)
Guiyang 4.2 9.6 13.9 183 10.5 112.8 20.7 7.3 266 Xiao et al. (2013)
Chengdu 5.1 6.6 1.4 197 16.2 150.5 8.9 156 213 Wang and Han (2011)
Lijiang 6.1 14.2 2.54 50.2 7.73 11.4 11.6 3.63 32.6 Zhang et al. (2012a)
Nam Co 6.6 19.7 14.5 15.4 65.6 7.4333 18.1 19.2 10.4 15.5 Li et al. (2007)
Tokyo 4.5 2.9 37 24.9 11.5 40.4 55.2 30.5 50.2 Okuda et al. (2005)
Spain 5.6 15.1 188 122 53.7 32.5 181 31.5 72.5 Moreda-Piñeiro et al. (2014)
Singapore 4.2 7.20 32.8 16.1 6.54 19.1 34.2 22.3 83.5 Hu et al. (2003)
New York 4.5 0.33 1.61 3.59 0.99 10.5 2.14 22.6 36.9 Ito et al. (2002)
Mexico 5.1 2.16 7.00 26.4 2.46 92.4 9.56 42.6 61.9 Báez et al. (2007)

([NO3- ? nssSO42-]) (Balasubramanian et al. 2001). If
FA = 1, it is considered that rainwater acidity generated by
SO42- and NO3- will not be neutralized at all. The annual
FA value in this study is less than 0.01, indicating that
more than 99 % acidity in the local rainwater was neu-
tralized by alkaline substances. The ([nssCa] ? [NH4?])/
([NO3- ? nssSO42-]) ratio was higher than one also
indicated that Ca2? and NH4? were sufficient to neutralize
the acidity in the region. The FA value in Xi’an was close
to that in most northern Chinese cities (Xu et al. 2009; Lu
et al. 2011), but much lower than that in most southern
Chinese cities (Zhang et al. 2007; Cao et al. 2009; Wang
and Han 2011; Xiao et al. 2013), indicating that there is a
large difference in neutralization ability of alkaline con-
stituents between northern and southern China. The relative
contribution of NO3- to the acidification, and [NO3-]/
([NO3- ? nssSO42-]) (Cao et al. 2009), indicated that
approximately 23 % of rainwater acidity was due to NO3-
and 77 % to nssSO42-. This value is basically the same
with that in some northern China cities (Xu et al. 2009;
Wang et al. 2012). NO3- in rainwater was the result of
homogenous and heterogeneous gas-phase transformations
of NOx (mainly from vehicles) to HNO3, followed by
reaction with NH3 to form NH4NO3 (Akpo et al. 2015).
Although H2SO4 is the primary contributor to rainwater
acidity in Xi’an, contribution of HNO3 was still relatively
high. From Fig. 4, it can be seen that the annual variation
of SO2 emissions in recent years was minor. This may be
related to the adjustment of energy structure and multi-
pollutant control strategy in Xi’an. But the motor numbers
increased rapidly from 1999 to 2012, and this may keep on
rising in the near future. Meanwhile, annual average ratio
of SO2/NO2 decreased rapidly from 1.3 in 2008 to 0.8 in
2013 (Fig. 4b). Thus, NOx emissions will continue to
increase and contribution of HNO3 to rainwater acidity in
Xi’an will be increased in the future.
Neutralization Factors (NF) were used to evaluate the
neutralization of rainwater by alkaline species, which are
calculated by the following equation (Budhavant et al.
2011; Paternoster et al. 2014):
NFXi ¼ ½nssXi =ð½NO 2
3 þ nssSO4 Þ;
where Xi is the chemical component of interest and all of
the ion concentrations are expressed in leq/L.
Since Na? and Cl- were mostly originated from sea in
the form of sea salt, their role in either acid production or
neutralization is negligible. Ca2?, Mg2?, and SO42- mea-
sured over land partially originated from sea in the form of
neutral salt, which did not play any role in deciding acidity/
alkalinity of the rainwater (Budhavant et al. 2011). Thus,
while defining acid NF of cations, only non-sea salt com-
ponent of Ca2?, Mg2?, K? and NH4? are considered. The
values of NF for Ca2?, NH4?, K? and Mg2? were 0.99,
0.50, 0.21 and 0.09, respectively, indicating that Ca2? and

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Fig. 4 Variations of industrial SO2 emissions and motor numbers (a),
and annual average ratio of SO2/NO2 in Xi’an (b). Data were from
Xi’an Municipal Bureau of Statistics (2000–2014). Industrial SO2
NH4? were the dominant neutralization substance in rain-
water and the contribution of K? and Mg2? to the overall
neutralization process was very low. The positive rela-
tionship between (Ca2? ? NH4? ? Mg2?) and
2- - 2
(SO4 ? NO3 ) (R = 0.96) also indicated that rainwater
acidity was neutralized by alkaline species. Compared with
cities in south China, Xi’an has the higher values of NF for
Ca2? and NH4?, especially Ca2? (Cao et al. 2009; Wang
and Han 2011; Wu et al. 2012; Xiao et al. 2013). It should
be stressed here that using NF to examine neutralization
effect of these cations on acids might be to some extent
overestimated, because alkaline species do not always fully
contribute to the neutralization process in rainwater (Huang
et al. 2008). The dominant neutralization role of Ca2? was
due to its high concentration and the high scavenging
efficiency of precipitation on the coarse mode particles. It
is well-known that, Xi’an is close to Loess Plateau and
some deserts. The soil dust from these areas can contribute
a large amount of alkaline material, especially Ca2?, to
neutralize the acidic ions. If all of the nssSO42- and NO3-
presented in free acid forms and were not neutralized by
alkaline species, the potential acidity could be estimated
using the sum of nssSO42- and NO3- in rainwater (Fujita
et al. 2000). In this study, the sum of VWM concentration
of nssSO42- and NO3- varied from 36.3 to 2884 leq/L,
with an average value of 556.5 leq/L. Based on the above
assumption, these values correspond to rainwater pH in the
range of 2.54–4.44, with a mean value of 3.25. It is obvi-
ously that if there were no Ca2? and NH4? components
present in the air, the rainwater acidity would remarkably
increase. In other words, in the absence of neutralization of
acidity, acid rainwater would widely occur in Xi’an.
Page 7 of 12 209
emissions varied insignificantly, motor numbers increased rapidly,
and SO2/NO2 ratio deceased in recent years
Origins of the major ions in rainwater
If the contributions from volcanic and other natural sources
are negligible, the ionic compositions in rainwater would
be mainly from anthropogenic sources, sea spray, and
terrestrial dust from weathering (Zhang et al. 2007; Cao
et al. 2009). Strong correlations were found between each
pair of ions (SO42-, NO3-, NH4?, Ca2?, and Mg2?) in
rainwater (Table 2), indicating that these ions may exist in
the following forms: CaSO4, MgSO4, (NH4)2SO4, NH4-
HSO4, Ca(NO3)2, Mg(NO3)2, and NH4NO3. Ca2? and
Mg2? are highly correlated due to their common occur-
rence in soil and dust. This was due to calcareous nature of
loess and the frequent input of soil dust during the spring
season in this area. The coexistence of SO42- and NO3-
may be attributed to the similarity of their chemical
behaviors in rainwater and atmospheric particles and to a
common source (coal combustion) of their precursors SO2
and NOx (Al-Khashman 2009).
Enrichment factors (EFs) are usually applied to identify
the source of ions in rainwater (Zhang et al. 2007; Cao
et al. 2009; Wang and Han 2011), which are based on the
elemental ratio found between ions collected in the atmo-
sphere or in rainwater, as compared to a similar ratio for a
reference material. Na is commonly taken as the best ref-
erence element for seawater since it is assumed to be of
purely marine origin (Samara et al. 1992). Al and Ca are
typical lithophilic elements normally used as reference
elements for continental crust, since their compositions in
soil, the only natural source for lithophilic elements, are
hardly changed (Cao et al. 2009). The EF values for rain-
water compositions were calculated using Na? as a
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209 Page 8 of 12 Environ Earth Sci (2016) 75:209

reference element for marine source and Ca2? for crustal to anthropogenic sources. Considering no NO3- from
source in this study, which are calculated as follows: marine source, contributions from anthropogenic sources
EFseawater ¼ ðX=Naþ Þrainwater =ðX=Naþ Þseawater were obtained by subtracting the soil contribution from that
of total NO3- in rainwater. Like SO42-, about 99.0 % of
EFcrust ¼ ðX=Ca2þ Þrainwater =ðX=Ca2þ Þcrust ; total NO3- attributed to anthropogenic sources. According
to the statistics, emission of SO2 and NOx in Xi’an in 2012
where X is the concentration of the ion of interest, X/Na?
was 83072.91 and 4186.71 t, respectively (XAMBS 2013).
of seawater is the ratio from seawater composition, and
In addition, civil vehicles in Xi’an in 2012 were 1.38
X/Ca2? of crust is the ratio from crustal composition.
million (XAMBS 2013). Extensive SO2 and NOx emitted
An EF much less than 1 or much higher than 1 is con-
into the atmosphere due to coal combustion and vehicles
sidered to be diluted or enriched relative to the reference
led to high content of SO42- and NO3- in rainwater.
source. The calculated EFseawater and EFcrust for SO42- and
Unlike SO42- and NO3-, Ca2? and K? are mainly of
NO3- are much higher than 1 (Table 4), indicating that
crustal origin (Table 5). Ca2? is mainly originated from
contributions of SO42- and NO3- from marine and crust
dust transported from the Loess Plateau and desert areas,
source are small. Thus, the SO42- and NO3- in rainwater
such as Taklimakan desert, Gurbantonggut desert, Badain
mainly come from anthropogenic sources, such as coal-
Jaran desert, Tungeli Desert and Muus Desert, as well as
fired power stations and traffic emission. The Cl- had
construction activities. The primary source of K? was
EFseawater and EFcrust value of 1.2 and 66.5, clearly indi-
considered to be terrestrial because it is difficult to distin-
cating its marine origin. The EFseawater and EFcrust for
guish the soil from the biomass combustion. About 73.3 %
Mg2? and K?, indicating that they were mostly originate
of Mg2? came from crust source and 26.7 % from marine
from crust source and partly from marine source (Table 4).
source. Approximately 86.6 % of Cl- was from marine,
It should be noted that the contributions shown in Table 4
12.0 % from anthropogenic sources, and only 1.4 % from
were a rough estimation, since various chemical and
crust.
physical processes, besides measurement uncertainties, can
Source identification of different chemical ions present
cause errors in the estimation.
in rainwater was further carried out through principal factor
To further estimate marine, crust and anthropogenic
analysis (PCA), which transformed a set of observed
contributions to different ionic species in rainwater, the sea
independent variables into an orthogonal set of variables
salt fraction (SSF) and the terrestrial fraction, including the
called principal components (Chidambaram et al. 2014;
crust fraction (CF) and the anthropogenic fraction (AF),
https://en.wikipedia.org/wiki/Factor_analysis). The first
were calculated by the following equations (Zhang et al.
principal component accounts as much as possible the
2007; Cao et al. 2009):
variance of the observed variants. The second principal
%SSF ¼ 100 ðX=Naþ Þseawater =ðX=Naþ Þrainwater component accounts for as much as possible the residual
%CF ¼ 100 ðX=Ca2þ Þcrust =ðX=Ca2þ Þrainwater variances not accounted by the first principal component,
%AF ¼ 100  %SSF  %CF and so on. Because of certain mathematical conditions such
as variance properties of the principal components, initial
It is revealed that nearly all the SO42-, NO3-, Ca2?, and factor loadings are unlikely to reveal the underlying
K appear to be of non-marine origin. SO42- had a minor
?
structure of the observed variants. To have a more clear
contribution from crust source, with about 96.0 % of it due view of this structure, common factors associated with

Table 4 Enrichment factors

SO42-/Na? Cl-/Na? Ca2?/Na? Mg2?/Na? K?/Na? NO3-/Na?
relative to seawater and crust for
rainwater constituent Seawatera 0.12 1.16 0.044 0.23 0.022 0.00002
Rainwater 6.03 1.34 6.53 0.86 0.78 1.6
EFseawater 50.3 1.2 148.4 3.7 35.5 80,000
SO42-/Ca2? -
Cl /Ca 2? ?
K /Ca 2?
Mg /Ca2? 2?
NO3-/Ca2?

Soilb 0.0188 0.0031 0.504 0.561 0.0021

Rainwater 0.92 0.21 0.12 0.13 0.21
EFcrust 49.2 66.5 0.2 0.2 98.1
a
Berner and Berner (1987)
b
Regard crust S and N as entire SO42- and NO3- compounds, respectively (Lu et al. 2011)

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Environ Earth Sci (2016) 75:209 Page 9 of 12 209

Table 5 Source contributions for different ionic constituents in loadings of all these ions have occurred in the same factor
rainwater of Xi’an on account of the fact that industrial activity gives way to
Ion Sea salt fraction Terrestrial fraction vehicular activity which causes stirring of soil dust raised
(%SSF) by the convective activity coupled with the dust driven by
Crust Anthropogenic source
fraction (%) fraction (%) vehicles themselves. Factor II explains 11.9 % of the total
variance, shows high loadings for pH and F-. High load-
SO42- 2.0 2.0 96.0 ings for pH is closely related to the neutralization process
NO3- 1.0 99.0 of the acidity of rains. High loadings for Ca2?, NH4?, and
Cl- 86.6 1.4 12.0 Mg2? also imply neutralization of acidity by alkaline
2?
Ca 0.7 99.3 substances. High loadings for F- may be related with
Mg2? 26.7 73.3 anthropogenic activity, such as combustion of coal with
K? 2.8 97.2 high fluoride contents, and production of brick and tiles
from clay with high fluoride contents.

initial set of loadings are linearly transformed into a new Backward trajectories
set of common factors, associated with new set of loadings,
factor rotation. Kaiser Normalization varimax rotation is The backward trajectories were modified based on the
used in this study, which yields set of loadings such as the HYSPLIT Model access via NOAA ARL READY Website
variances of loadings are maximum. The factor loadings were used to deduce the probable source regions of the air
showed the data synthesized into two factors (Table 6). masses from which rainwater samples derived (http://www.
Factor I explains 69.5 % of the total variance, character- arl.noaa.gov/HYSPLIT.php). Administration trajectories
ized by high loading of EC, Ca2?, Mg2?, NH4?, SO42-, for time periods of 72 h were computed for 500, 1000 and
NO3-, Cl-, K?, and Na?. It demonstrates a well mixed 3000 m above ground level (AGL). They correspond to
source influenced by crustal, anthropogenic, and marine 950, 850, and 700 hPa, respectively, barometric levels at
origins, possibly transported over a long distance. As the end point of the trajectories. The trajectories were
mentioned earlier, the source for Ca2? and Mg2? is the soil calculated for every rainwater-sampling day. According to
and dust. Na? and Cl- occur in the form of sea salt. the 500 and 1000 m AGL backward trajectories, the air
Vehicular with emission from industries is the sources of mass in the rainy days at Xi’an can be divided into four
SO42- and NO3-. High loadings for NH4? and K? imply clusters (Fig. 5). Air masses in Cluster 1 were from
that they might have been associated with waste biomass Northwest China (Fig. 5a, b), including Xinjiang, Gansu,
burning and decomposition of vegetation waste. The Qinghai, and Neimeng. These air masses can bring higher
amounts of Ca2? and Mg2? through long-distance trans-
mission, which can neutralize acids in rainwater. Air
Table 6 Varimax principal component loadings from rainwater masses in Cluster 2 were from East China (Fig. 5c, d). The
samples sources beneath these winds are from heavily industrialized
Chemical variable Principal component areas, which could emit considerable amounts of anthro-
pogenic pollutants. Air masses in Cluster 3 were from
1 2
South China (Fig. 5e, f), including Sichuan, Chongqing,
pH 0.41 0.86 Guizhou, and Yunnan. Air masses in Cluster 4 were from
TDS 0.80 -0.14 local areas (Fig. 5g, h).
EC 0.94 -0.15
K? 0.84 -0.16 Estimation of wet deposition of nitrogen and sulfur
Na? 0.82 -0.02
Ca2? 0.95 -0.11 The interest in nitrogen and sulfur deposition is increasing
Mg 2?
0.89 -0.10 because of their importance as nutrient resources and major
NH4? 0.98 -0.06 components of acid deposition within the overall global
F- 0.56 0.76 nitrogen and sulfur cycle (Huang et al. 2010). The annual
Cl- 0.74 0.02 sulfur, nitrogen and calcium wet deposition was calculated
NO3- 0.89 -0.09 based on their VWM concentrations multiplied by annual
SO42- 0.97 -0.06 precipitation (Liu et al. 2013). The annual wet deposition
% of variance 69.5 11.9
of sulfur, nitrogen and calcium in Xi’an was 3.9, 1.5, and
Cumulative variance 69.5 81.4
4.2 t/km2, respectively (Fig. 6). The NH4-N (1.0 t/km2)
deposition was two times that of the NO3-N (0.5 t/km2)

123
209 Page 10 of 12
Fig. 5 Typical trajectories for rain events associated with air masses
coming from the four defined sectors. a, b Northwest China; c, d East
China; e, f South China; g, h local area; red triangles trajectories
deposition in Xi’an. Compared with other cities in China,
the deposition of NH4-N, NO3-N and total inorganic
nitrogen (TIN) in Xi’an was the lowest among these four
cities, and the sulfur deposition is in the medium range,
higher than Beijing and Shanghai, but lower than
Guangzhou (Fig. 6). From Fig. 6, it can be roughly
deduced that effect of wet deposition of N and S for
Fig. 6 Annual wet deposition of sulfur and nitrogen in Xi’an, Beijing
(Yang et al. 2004), Shanghai (Huang et al. 2008), and Guangzhou
(Huang et al. 2010)
123
Environ Earth Sci (2016) 75:209
arriving at an altitude of 500 m; blue squares trajectories arriving at
an altitude of 1000 m; green circles trajectories arriving at an altitude
of 3000 m
ecosystem in southern China might be greater than that in
northern China.
Recommendations
As mentioned above, Ca2? played an important role in
neutralizing rainwater acidity in Xi’an and even in northern
China. The increase of dust events and construction
activities can increase Ca2? in rainwater, which were
beneficial in reducing acid rain, but were adverse to air
quality. Similarly, reducing emissions of particles could
offer more clear-sky and improve air quality, but poten-
tially lead to enhanced acid rainwater. In Xi’an, measures
have been taken to reduce particle concentrations in air,
which are likely to continue for some time. This will lead
to reduced calcium deposition and improve air quality. But
if sulfur and nitrogen deposition is not reduced at a similar
or higher rate, rainwater acidity will be enhanced, which is
harmful to ecosystems. Therefore, how to balance the
relationship between acid rainwater and dust pollution in
Xi’an is worthy of studying. The simultaneous reduction of
particle emissions and the limitation of fossil fuel and
vehicles emissions are worthy of advocating. But their
exact reduction ratio is still unknown.
Environ Earth Sci (2016) 75:209
Conclusions
Investigation of chemical composition of rainwater was
carried out in Xi’an. The rainwater possessed relatively
high major ions concentrations comparing with other sites
in China and in the world. Ca2?, NH4?, SO42-, and Cl-
accounted for 78 % of the total ions. Although the con-
centrations of SO42- and NO3- were very high, rainwater
in Xi’an was alkaline, similar to what was observed in
other semi-arid and arid areas around the world. This
indicated the acid rain events were not serious, which was
mainly attributed to the neutralization of the acidity by
alkaline ions of Ca2? and NH4?. Major ionic concentra-
tions in rainwater were high in spring and winter and low in
summer and autumn. High enrichment factor of seawater
for SO42-, NO3-, Ca2? and K? indicated that large
amounts of these ions mainly originated from a non-marine
source. Similarly, high enrichment factor of soil for SO42-,
NO3-, and Cl- suggested that most of these ions did not
come from soil source. Sea salt fraction, crust fraction, and
anthropogenic source fraction were further estimated. The
results show that Ca2? and K? are mainly of crustal origin
from soil and dust, Cl- is from marine, Mg2? is mainly
from crust source and part from marine source, and SO42-
and NO3- are mostly attributable to anthropogenic sources
of local coal combustion and vehicle exhaust. Wet depo-
sition of nitrogen in Xi’an was in the low range while
sulfur deposition is in the medium range compared with
other cities in China. The coupled analysis of the rainwater
chemical content and air mass back-trajectories suggests
that the impact of pollution transport from local and distant
emission sources is important at the investigated site.
Compared with other selected sites worldwide, Xi’an is
severely polluted due to high coal combustion and vehicles
emissions. In the future, rainwater acidity due to HNO3
may increase because of the increasing trends of NOx and
relatively stable trends of SO2 emissions in Xi’an. Thus,
fossil fuel and vehicles emissions must be limited. The
results from the present study provide useful scientific
evidence for making emission-control policies in Xi’an.
Acknowledgements This work was financially supported by Youth
Innovation Promotion Association of CAS (2015336), Shaanxi
National Science Foundation (No. 2015JM4131), and the Key
Research Program of the Chinese Academy of Sciences (Grant
KZZD-EW-04-02). Appreciation is expressed to Executive Editor and
the anonymous reviewers for insightful suggestions.
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