Journal of the Air & Waste Management Association

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The effect of atmospheric particulates on the

rainwater chemistry in the Yangtze River Delta,
China

Yan Han, Hong Xu, Xiaohui Bi, Fengmei Lin, Li Jiao, Yufen Zhang & Yinchang
Feng

To cite this article: Yan Han, Hong Xu, Xiaohui Bi, Fengmei Lin, Li Jiao, Yufen Zhang & Yinchang
Feng (2019) The effect of atmospheric particulates on the rainwater chemistry in the Yangtze
River Delta, China, Journal of the Air & Waste Management Association, 69:12, 1452-1466, DOI:
10.1080/10962247.2019.1674750

To link to this article: https://doi.org/10.1080/10962247.2019.1674750

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JOURNAL OF THE AIR & WASTE MANAGEMENT ASSOCIATION
2019, VOL. 69, NO. 12, 1452–1466
https://doi.org/10.1080/10962247.2019.1674750

TECHNICAL PAPER

The effect of atmospheric particulates on the rainwater chemistry in the Yangtze

River Delta, China
a,b
Yan Han , Hong Xua,b, Xiaohui Bia,b, Fengmei Linc, Li Jiaoc, Yufen Zhanga,b, and Yinchang Fenga,b
a
College of Environmental Science and Engineering, Nankai University, Tianjin, People's Republic of China; bThe State Environment
Protection Key Laboratory of Urban Particulate Air Pollution and Prevention, Tianjin, People's Republic of China; cThe Environmental
Monitoring Center of Hangzhou, Hangzhou, People's Republic of China

ABSTRACT PAPER HISTORY

To investigate the effect of atmospheric particulates on the chemistry and acidity of rainwater during the Received March 8, 2019
washout process in areas with highly acidic rainfall, rainwater and particulates (before, during and after Revised September 6, 2019
rain) were sampled and analyzed from June 2008 to June 2009 in the Yangtze River Delta region, China. Accepted September 13, 2019
The volume-weighted mean pH of the rainwater was only 4.44 in Hangzhou, and the average concentra-
tions of TSP (total-suspended particulates) and PM10 (particulates with aerodynamic equivalent diameters
of less than 10 μm) during the study period were 191 μg/m3 and 155 μg/m3, respectively. The measured
acid buffering capacities of PM10 and TSP were 1.31 ± 0.45 and 1.61 ± 0.84 ml/mg, on average,
respectively, indicating that both had a certain acid buffering capacity. Rain appeared to have
a pronounced scouring effect on particulates, except for F− and Cl− in PM10. Upon combining the
correlation analysis between ions in particulates and rainwater with Enrichment Factor and Principal
Component Analysis of the rainwater chemistry, the results suggested that the components of rainwater
were mainly derived from washout processes acting on particulates from crustal dust and building
industry sources (Ca2+), marine sources (Na+, K+ (in spring), Mg2+ and Cl−) and anthropogenic sources,
especially secondary aerosols emitted from agricultural land, motor vehicles and industrial plants (NO3−,
SO42-, and NH4+). The F− in rainwater was mainly contributed by gaseous pollutants, such as HF from
cooling systems, coal burning and surrounding factories.
Implications: The interaction between particulates and rain in areas with highly acidic rainfall
include the following: rain appears to have a pronounced scouring effect on most components in
the particulates; the components of the rainwater are mainly derived from washout processes
acting on PM contributed by crustal dust, sea salt and secondary aerosol subcloud; and the acid
buffering capacities of PM10 and TSP in Hangzhou are 1.31 ± 0.45 and 1.61 ± 0.84 ml/mg,
respectively, and had a certain acid buffering capacity toward rainwater.

Introduction
Air pollution in China is very complex because of the
large amounts of gaseous and particulate emissions. Acid
rain, ozone and particulate (hereafter referred to as PM)
pollutions coexist in some regions, especially in South
China (http://www.mee.gov.cn/hjzl/zghjzkgb/
lnzghjzkgb/). PM is commonly from motor vehicle
exhaust, industrial emissions, coal burning, and dust, as
well as from secondary pollution (Liu et al. 2017; Shi et al.
2014; Tian et al. 2016), and can be removed by wet and
dry deposition (Duhanyan and Roustan 2011; Zhang et al.
2018). Acid rain is mainly caused by acidic gases, such as
SO2 and NOX, which are mostly contributed by anthro-
pogenic sources including the burning of fossil fuels and
industrial chemical processes (Likens and Bormann 1974;
Mihajlidi-Zelić et al. 2006; Wang et al. 1993; Zhang et al.
2012a). The chemical characteristics of dry and wet
depositions can provide important information on atmo-
spheric pollution sources and help to control air pollu-
tion. However, the area with highly acidic rainfall in
China does not completely overlap with areas containing
high concentration of SO42- and NO3−. According to the
1990–1992 statistics of 27 major cities (11 in the north and
16 in the south, with most of the cities being provincial
capitals), it has been found that the sum of the SO42- and
NO3− annual concentrations in rainwater in the nonacid
rain region in northern China was 241.5 μeq/L (ranging
from 12.5 to 639.2 μeq/L), but in rainwater in the acid rain
region in southern China, that concentration was 145.1
μeq/L (ranging from 53.6 to 433.1 μeq/L); The sum of the

CONTACT Xiaohui Bi envbixh@126.com College of Environmental Science and Engineering, Nankai University, No.38 Tongyan Road, Jinnan District,
Tianjin 300350, People’s Republic of China
Color versions of one or more of the figures in the paper can be found online at www.tandfonline.com/uawm.
Supplemental data for this article can be accessed on the publisher’s website.
© 2019 A&WMA
 JOURNAL OF THE AIR & WASTE MANAGEMENT ASSOCIATION
Ca2+, Mg2+ and NH4+ annual concentrations in the
northern nonacid rain region was 575.6 μeq/L (ranging
from 64.1 to 799.7 μeq/L), but in the southern acid rain
region, it was 198.8 μeq/L (ranging from 55.7 to 436.4
μeq/L) (Wang et al. 1993). The situation has not changed
much in the last decade or so, as the sum of the SO42- and
NO3− annual concentrations in rainwater of the nonacid
rain region in northern China was 258.1 μeq/L (ranging
from 132.1 to 399.6 μeq/L) and the sum of the Ca2+, Mg2+
and NH4+ annual concentrations was 646.9 μeq/L (ran-
ging from 512.5 to 989.7 μeq/L) (Wang et al. 2019; Xu
et al. 2009; Zhang et al. 2003), but in rainwater of the acid
rain region in southern China, those concentrations were
260.1 μeq/L (ranging from 140.5 to 352.6 μeq/L) and
306.0 μeq/L (ranging from 140.0 to 447.5 μeq/L) (Han
and Liu 2006; Huang et al. 2008; Tu et al. 2005; Wang and
Han 2011; Zhang et al. 2007). The main reason for the
absence of regional acid rain pollution in the northern
region of China is that the atmospheric particulate matter
in the northern region is highly alkaline, which neutralizes
the acidity of rainwater and reduces the incidence of acid
rain in northern cities (Wang et al. 2009).
The formation processes of acid rain include the
rainout process in clouds and the washout processes
acting on gases and PM subcloud (Zhang et al. 2018).
Rain is an effective way to remove aerosol from the
atmosphere (Tang et al. 2005; Zhang et al. 2007), and
accordingly, atmospheric aerosol also has a great influ-
ence on the composition and acidity of rainwater (Huo
et al. 2012). The chemical compositions of cloud water
and rainwater have been compared within southwes-
tern China, such as Chongqing City and Guizhou
Province in China, which experienced severe acid rain
pollution in the 1980s and 1990s (Huang et al. 1995; Lei
et al. 1997, 2001). It was found that washout processes
neutralized a large proportion of rainwater acidity
through the scavenging effect on alkaline PM subcloud
(Wang et al. 2009). The chemical constituents of PM in
China have changed a lot during the last 10 years, as
sulfate and nitrate are the major components in both
northern and southern China, with less alkali material
now (Liu et al. 2019; Meng et al. 2019). The decrease of
the particulate concentration and changes in its chemi-
cal constituents are very likely to be accompanied by
the emergence of another potential environmental pro-
blem: acid rain pollution in northern China will gradu-
ally become more prominent (Liu et al. 2019), which is
a problem that has to be taken seriously (http://www.
mee.gov.cn/hjzl/zghjzkgb/lnzghjzkgb/).
In this study, our attention was focused on the sub-
cloud scavenging process and its influence on PM and
rain. Some studies, such as those by Huo et al. (2012), Ren
et al. (2011) and Singh, Elumalai, and Pal (2016), have
1453
focused on the acid buffering capacity of PM, defining the
acid buffering capacity of PM according to the amount of
acid or alkali added into a PM solution before the pH
value reached 5.60. In this study, a similar calculation
method for the acid buffering capacity was used.
Hangzhou has been included in acid rain-control
areas by China’s Ministry of Ecology and Environment
(MEE) due to the low pH value (annual average of 4.4)
of rainwater and the high acid rain rate (80%), which
was calculated by the ratio between acid rain events with
a pH lower than 5.6 and the total rain events (Li and
Liang 2011). In the most recent 5 years, Hangzhou has
still been impacted by acid rain events and is where the
most serious acid rain has been found (Figure 1). The
aims of this study are: (1) to explore the scavenging
effects of rain on PM subcloud; (2) to provide basic
information for use in controlling PM and acid rain
pollution; and (3) to provide data and theoretical sup-
port for constructing the Acid Wet Deposition
Predicting and Forecasting (AWDPF) system. As China
increases its efforts to control particulate pollution, the
acid rain problem will probably be aggravated in some
areas, which is an effect that needs to be considered at
the same time. This AWDPF system is important for
both acid rain areas, such as Hangzhou, and nonacid
rain areas, such as North China.
Experimental methods
Study area
The Yangtze River Delta region is one of the most
developed areas in China and includes Shanghai,
Jiangsu and Zhejiang, which are also important inter-
sections of the “One Belt And One Road” and Yangtze
River economic belt. Hangzhou, the capital city of
Zhejiang Province in China, is located on the west
side of Hangzhou Bay near the East China Sea and is
very close to Shanghai (Figure 2), with a total area of
16,600 km2 (Yue, Liu, and Fan 2013), of which approxi-
mately 48.2% is urban area. It is a metropolitan city
with 9,188,000 inhabitants, of which ~80% are urban
residents, while ~20% are rural residents, and the urban
population is growing rapidly (http://www.hzstats.gov.
cn/tjnj/nj2017/index.htm, 2017). Hangzhou has
a subtropical, monsoonal climate with four distinct
seasons, characterized by a hot, humid summer
(June–August) and a cold, wet winter (December–
February) (Li and Liang 2011). The annual average
temperature, rainfall and relative humidity are 17.5°C,
1454 mm and 70.3%, respectively (Xu et al. 2011).
Hangzhou is a typical tourism city, and series of inter-
national conferences and activities have been
1454 Y. HAN ET AL.

Figure 1. The annual average pH distribution of precipitation in China in 2017.

Figure 2. Map of the study area and sampling site.

conducted here. Although the air quality is above that and ozone pollution (Figure 1), even though precursors
in middle China, acid rain has been an environmental such as SO2 have recently decreased (http://www.mee.
problem in the area for many years, together with PM gov.cn/hjzl/zghjzkgb/lnzghjzkgb/). Generally, with
 JOURNAL OF THE AIR & WASTE MANAGEMENT ASSOCIATION
conditions similar to those in many contiguous areas at
mid-low latitudes, Hangzhou can represent the charac-
teristics of the Yangtze River Delta urban agglomera-
tion, so this study can provide a good reference for
these areas in the control of air pollution.
Rainwater sampling
The sampling site is shown in Figure 2, and it is located in
the urban area of Hangzhou and influenced by high levels of
human activity. Two power plants lie to the north (12 km)
and south (20 km) of the sampling site, respectively.
Agricultural land is mainly located in the east, southeast
and northwest of the sampling site. Typical industrial areas
are located in the north (characterized by steelworks, cement
plants, chemical industry, etc.), west (characterized by plas-
tic plants, pharmaceutical factories, shipyards, machinery
works, etc.), southeast (characterized by textile mills, print-
ing and dyeing mills, chemical fiber factories, etc.), and east
(characterized by building materials and paint factories,
among others), respectively. The East China Sea is approxi-
mately 130 km away from the sampling site. The sampling
campaign was carried out from June 2008 to June 2009 on
the roof of a building at the Hangzhou Environmental
Monitoring Center (30°16′N, 120°08′E), which is approxi-
mately 4 m up from the ground level, and this location
conforms to the specifications for rain monitoring (Allan
2004). An automatic rainwater sampler equipped with
a polyethylene bucket (SZG-Ш, China) was set at the height
of 1.5 m above the roof, and at least two more polyethylene
buckets (with a diameter and height of 20 cm) were pre-
pared at the sampling site. The sampling buckets and rain-
water containers were cleaned using diluted HCl (10%) first,
washed with deionized water until the Cl− in the waste water
was at the same concentration as that of the deionized water,
and then dried before using. Rainwater sampling started
when rain occurred and ended when rain stopped, and the
plastic cover of the rainwater sampler was removed imme-
diately after the first raindrops to prevent contamination
from dry deposition. If several rain events happened in
1 day, the rainwater from 8:00 a.m. on that day until 8:00
a.m. on the next day were merged into one sample, and each
24-h rainwater sample was treated individually. A rain
gauge was used to calculate the rain amount, and 101 rain-
water samples were collected in total. The electric conduc-
tivity (EC) of the rainwater samples was measured with
a conductivity meter (DDS-307, Leici Corp., Shanghai,
China) which has a measurement range of 0 ~ 105 μS/cm.
A pH meter (Mettler Toledo Delta 320) with a flow-type
combination electrode was used for pH measurements, and
two standard buffer solutions at pH 4.01 and 6.86 were used
for pH calibration before the measurement. The sampled
rainwater was filtered through a 0.45-μm millipore
1455
membrane filter to remove insoluble substances and then
shifted to polyethylene bottles for storage in a 4°C refrig-
erator after in situ conductivity and pH measurements.
Air particulate sampling
Four particulate middle-flow impact samplers (Wuhan
Tianhong Intelligent Instruments, Inc. China, TH-
150C, flow rate: 100 L/min) were employed for TSP
and PM10 sampling on the same building roof of the
rainwater sampling site, with two used for the TSP and
two used for the PM10. PM sampling each day
occurred over 23 h from 8:00 a.m. to 7 a.m. of the
next day. The TSP and PM10 were collected on both
pre-weighed polypropylene fiber and quartz fiber filter
membranes. The membranes were weighed using an
analytical balance with a reading precision of 1 μg after
stabilization under constant temperature (20 ± 5°C)
and humidity (40 ± 2%) for 48 h. A total of 148 PM
samples including 74 TSP samples and 74 PM10 sam-
ples were collected, among which 45 TSP and 50 PM10
samples were characterized before, during, and after
the rain events. The reason for only part of the pre-
cipitation events having PM samples that covered the
three stages (before, during & after each rain event)
was that PM sampling was manually operated, while
rainwater was automatically sampled. On some days,
the start time of PM sampling was missed for some
rain events, so PM samples were absent during these
rain events. Each rainy day was treated individually,
and the “PM samples during rain” were those sampled
from 8:00 a.m. of each rainy day to 7:00 a.m. of the
next day, while the PM samples collected on the day
before each rainy day were “before rain samples”,
regardless of whether it rained during in the day before
each rainy day. The same was true for the “after rain
samples”, as long as the samples were collected on
the day after a rainy day. The following is an example
illustrating the timing of samples before, during and
after rain events: for the rain event that happened on
Mar. 3, 2009, “before” includes PM samples collected
on Mar. 2, 2009; “during” includes PM samples col-
lected on Mar. 3, 2009; and “after” includes PM sam-
ples collected on Mar. 4, 2009. All PM samples were
stored in a 4°C refrigerator after the weighing
procedure.
Methods for chemical analysis
Among the 101 rainwater samples, only 34 were ana-
lyzed for chemical compositions, and the remaining
samples were used for measuring only the pH and
conductivity, of which 31 contained monitored PM
1456 Y. HAN ET AL.
samples that covered all or part of the three periods
(before, during and after rain). Four anions (SO42-,
NO3−, F−, Cl−) and five cations (NH4+, K+, Ca2+,
Na+, Mg2+) in rainwater and PM samples were quanti-
tatively analyzed using ion chromatography (Dionex-
120, USA). The ion chromatograph was calibrated with
standard reagents that covered five concentration gra-
dients for each ion, and this calibration procedure was
conducted each week to guarantee the accuracy of the
measurements. For the PM samples, one-eighth of the
polypropylene membrane was cut off and used for
water-soluble ions analysis.
The acid buffering capacity was calculated using the
following formula (Huo et al. 2012; Ren et al. 2011):
Ai ¼ ½ð10pH0  V0  10pH1  V1 Þ=mi =R0 (1)
A ¼ Ai (2)
pOH0 pOH1
Aj ¼ ½ð10  V0  10  V1 Þ=mj =R0 (3)
A ¼ Aj (4)
where A is the acid buffering capacity expressed in ml/mg,
for which positive value (Ai) represents the volume of HCl
acid standard solution (10−4 N, pH = 4.0) that the PM
could neutralize to 7.00 per milligram PM, while
a negative value (-Aj) represents the volume of HCl acid
standard solution that has the same acidity per milligram
PM. The standard HCl acid solution was used as the
titrant in the first case (in equations (1) and (2)), and
the standard NaOH alkaline solution (10−4 N, pH = 10.0)
was used as the titrant in the second case (in Equations (3)
and (4)). Each intersecting PM sample (one-fourth of the
whole PM sample was used in the measurement of the
PM acid buffering capacity) was dissolved in 10 ml ultra-
pure water and filtered through a 0.45-μm millipore
membrane filter. In the first case, pH0 = 4.0 represents
the initial pH of the HCl acid solution and pH1 represents
the final pH of the mixed solution after the HCl acid
solution was reacted with the PM solution. mi is the PM
mass in 10 ml PM solution. R0 = 10−4 mol/L, representing
the H+ (HCl) ion concentration of the titrant. In
the second case, pOH0 = 4.0 (pH0 = 10.0) represents the
initial pOH of the NaOH alkaline solution and pOH1
represents the final pOH of the mixed solution after the
NaOH alkaline solution was reacted with the PM
solution. mj is the PM mass in 10 ml PM solution.
R0 = 10−4 mol/L, representing the OH− (NaOH) ion
concentration of the titrant. V0 is the volume of the titrant
(standard HCl acid or NaOH alkaline solution) used in
each case, and V1 is the final volume of the mixed solution
when the titration was performed.
Enrichment factor (EF) calculation
The enrichment factor (EF) is typically used to identify
the origins of chemical components in rainwater, and
in the present study, Na+ was used as the reference
element for marine sources. The EF of an ion in rain-
water relative to the ion in seawater (EFseawater) was
calculated according to the following equation (Wang
et al. 2019):
   
X X
EFseawater ¼ = (5)
Naþ rainwater Naþ seawater
where X is the ionic concentration of interest
(X/Na+)rainwater is the ratio of the rainwater compo-
sition, and (X/Na+)seawater represents the ratio of the
seawater composition.
Results and disscussion
Acidity and ionic composition of rainwater
The seasonal variations of the pH, EC and major ions
are displayed in Table 1. First, the balance between the
cations and anions was assessed according to the ratio
of ∑C/∑A, which was within the range of 1 ± 0.25
(Keene et al. 1986) in this study, indicating that the
data quality was acceptable. The rainfall amount
throughout the year was 1199.3 mm, which was com-
parable to the perennial average annual rainfall
(1454 mm) and showed that most of the rain had
been captured. The highest amount occurred in sum-
mer (493.2 mm), which was almost 2.5 times that in
winter (202.1 mm) and 2 times that in spring
(258.4 mm) and autumn (245.6 mm). The higher the
ion concentration, the higher was the conductivity.
A large-scale rain of drizzle type can scavenge more
aerosol than can localized heavy rain, and this can be
attested by the volume-weighted mean EC values in
Table 1. A higher EC was found in winter rainwater
than in rainwater during the other three seasons, and
the EC and ∑C, ∑A of summer rainfall were the lowest.
Because of the weak convection of air masses during
winter, most of the pollution was trapped in the lower
boundary layer, unlike in summer, causing the slow
removal of large concentrations of trapped pollution
in the boundary layer with no dilution effect compared
to that in summertime, which finally resulted in rela-
tively higher ion concentrations in winter, as reflected
by the EC (Zhang et al. 2007). Here, the inconsistency
between the total ion concentrations and EC values
among seasons in Table 1 was because not all the rain-
water samples were analyzed for chemical composi-
tions. The pH values of rain during the study period
 JOURNAL OF THE AIR & WASTE MANAGEMENT ASSOCIATION 1457

ranged from 3.85 to 6.73, with a volume-weighted

∑C/ ∑A
1.13
1.09
1.05
1.25
1.08
mean (VWM) of 4.44, which was a bit lower than the
pH observed (4.50) by Xu et al. (2011) in Hangzhou.

238.2 (95.4)

212.0 (72.4)
187.8 (26.7)
170.9 (102)
The pH value order was summer > spring > autumn >

∑A
winter, indicating that the acid rain status was the most

190.2
severe during the winter time, and the possible reason
for this result was the higher acid gas concentrations

186.0 (105.8)
268.6 (59.1)

221.8 (36.9)
234.5 (0.9)
during this season (Tang et al. 2005; Wang et al. 1993).
∑C
As shown in Figure 3, the pH values of rainwater were

204.8
relatively lower and fluctuated a lot during summer but
132.4 (58.1)
119.1 (77.9)
125.7 (20.4)
99.9 (8.5)
were more stable in winter than during the other three
SO42-

122.4 seasons. It was also found that there was a longer

period of duration of rain during winter, which was
possibly because the type of rain was more likely to be
62.5 (22.2)
32.6 (19.1)
54.4 (14.3)
47.5 (20.0)

from non-convective stratiform rain covering large

NO3−

areas (such as the entire city or province) during this

42.4
Water soluble ions (μeq/L, mean(SD*), Num. = 34)

season, and this was opposite to the short periods of

12.7 (10.6)
35.5c(8.0)

thunderstorms and locally heavy rain in summertime.

23.3 (2.9)
30.2 (0.3)
Cl−

In addition to the different rain patterns among the

18.1

seasons, the land surface became wet when it rained

8.7 (23.1)

and less soil dust went into the air, but the anthropo-
7.8 (7.1)
6.5 (5.4)

10.2 (0.9)
F−

genic emissions of acid gases such as SO2 and NOX

7.3

were not influenced. As mentioned above, the accumu-

lation of high levels of pollution, especially acid gases,
37.2 (29.9)
52.3 (9.2)

50.4 (4.2)
92.2 (0.4)
Ca2+

along with slow drizzle over longer periods can lead to

42.9

lower pH values during winter in Hangzhou.

Approximately 87.1% of the rain had a pH value of
6.2 (3.0)
3.7 (4.1)
2.6 (3.5)
18.9 (0.4)
Mg2+

less than 5.60%, and 52.5% has a value of less than 4.50.
3.6

The EC of rainwater ranged from 10.0 to 235.0 μS/cm,

with a VWM value of 43.1 μS/cm. The EC was approxi-
7.2 (39.6)
5.5 (0.7)
4.2 (3.4)

8.6 (6.8)

mately 2.1 times that measured in Jinhua City (20.3 μS/

K+

5.3

cm) near Hangzhou (Zhang et al. 2007, 2012b), indicat-

ing that the air pollution in Hangzhou was more ser-
112.5 (37.2)
91.6 (56.0)
102.8 (6.1)
40.5 (4)

ious than that in Jinhua.

NH4+

97.1

NH4+ and SO42- were the most important cation and

Table 1. Seasonal variation of rainwater chemistry in Hangzhou.

anion in rainwater, respectively. Ca2+ and NO3− had

57.9 (25.2)
4.1 (11.4)
10.1 (12.9)

comparatively equivalent concentrations as the second-

12.5 (8.0)
Na+

most important cation and anion. Unlike the average

10.6
Notes. *The values in the brackets are standard deviation (SD)

concentrations of water-soluble ions in rain in China

34.2 (34.3)
45.1 (33.5)
48.7 (10.4)
61.8 (15.1)

overall, rainfall in Hangzhou was more abundant in

NH4+ and SO42- instead of Ca2+ and SO42- (http://
H+

45.4

www.mee.gov.cn/hjzl/zghjzkgb/lnzghjzkgb/), which
will lead to more acidic rain. The highest ion concen-
μS/cm
43.7
34.3
39.5
58.3
43.1
EC

tration occurred in spring, which may have been caused

by transported dust from northern and northwestern
4.52
4.53
4.35
4.15
4.44
pH

China (Kang, Zhang, and Liu 2002), while the lowest

ion equivalent concentration in summer time was due
Rainfall.

258.4

245.6
202.1
1315.1
mm

609

to a large amount of rainfall (Zhang et al. 2007).

Num.
24
38
20
19
101

Scouring effect of rain on particulates

Season

The scouring effect on particulates exerted by rain was

Sum.

Total
Win.
Aut.
Spr.

investigated by analyzing the variation of the PM

1458 Y. HAN ET AL.

8 80 8 80
7
pH Spring Rainfall(mm) pH pH Summer
7

Rainfall (mm)

Rainfall (mm)
6 6
5 5
4 4
3 3
2 2
1 1
0 0 0 0
3/2/09

3/3/09

3/4/09

3/5/09

4/1/09

4/4/09
3/11/09

3/12/09

3/13/09

3/21/09

3/23/09

3/26/09

3/27/09

3/28/09

4/12/09

4/13/09

4/19/09

4/23/09

4/24/09

5/16/09

5/19/09

5/20/09

5/23/09

5/25/09

6/7/08
6/8/08
6/9/08

7/2/08

8/2/08
8/3/08
8/9/08

6/2/09
6/9/09
6/10/08
6/13/08
6/17/08
6/18/08
6/22/08
6/23/08
6/24/08
6/26/08
6/27/08
6/29/08

7/11/08
7/12/08
7/19/08
7/28/08
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7/30/08
7/31/08

8/11/08
8/15/08
8/22/08
8/23/08
8/24/08
8/25/08
8/29/08
8/31/08

6/13/09
6/20/09
6/27/09
6/30/09
8 80 8 80
7
pH Autumn 7
pH Winter

Rainfall (mm)

Rainfall (mm)
6 6
5 5
4 4
3 3
2 2
1 1
0 0 0 0
9/5/08

9/6/08

1/6/09

2/2/09

2/4/09
10/22/08

10/25/08

10/29/08

10/30/08

11/17/08

11/22/08

11/23/08

12/27/08

12/28/08
9/13/08

9/14/08

9/20/08

9/24/08

9/26/08

10/4/08

11/1/08

11/2/08

11/5/08

11/6/08

11/7/08

1/19/09

1/21/09

1/29/09

2/16/09

2/17/09

2/18/09

2/19/09

2/22/09

2/23/09

2/24/09

2/25/09

2/26/09

2/27/09

2/28/09
Figure 3. Seasonal variation of rainwater pH and rainfall in Hangzhou from June 2008 to June 2009.

(including the concentration, chemical compositions, a “before rain event”, precipitation would inevitably
and acid buffering capacity) during the three periods corresponded to a decrease of the particle concentra-
associated with rain events (before, during, and after tion. However, when it rained on the day of a “before
rain). rain event”, changes in the particulate matter were less
systematic. The effect of rainfall on the PM concentra-
Concentration variation of particulates tion was also important. It was not difficult to find that
A total of 31 rain events was chosen to analyze the both the TSP and PM10 concentrations went down
interaction between rain and particulate matter based during most rain, especially during events with large
on whether PM samples were available for the three amounts of rainfall. The decreasing rate of the TSP
defined periods. If the PM samples met one of these concentration ranged from 14.5% to 87.6%, and that of
three groups – “before-during”, “during-after”, and PM10 ranged from 5.3% to 86.6%, suggesting that wet
“before-during-after” – this rain event and the corre- deposition had a strong scavenging effect on PM
sponding PM samples could be used to analyze the (Blanco-Becerra et al., 2015; Duhanyan and Roustan
changes of the chemical composition of PM caused by 2011; González and Aristizábal 2012). In addition, the
rain. Figure 4 shows the variations of concentration and PM concentration before a rainy day was also impor-
acid buffering capacity of PM10 and TSP during the tant to the PM variation, and both PM10 and TSP
three periods. When it did not rain on the day of showed the largest decreasing rate when the PM

1500 50
Rainfall TSP PM10
PM concentration

Rainfall (mm)

1000
(µg/m³)

500

0 0
8.0 50
Acid Buffering Capacity

Rainfall (mm)

6.0
(ml/mg)

4.0

2.0

0.0 0
6/10/08
6/11/08
6/12/08
6/13/08
6/14/08

6/16/08
6/17/08
6/18/08
6/19/08

6/23/08
6/24/08
6/25/08
6/26/08
6/27/08
6/28/08

2/15/09
2/16/09

2/21/09
2/22/09
2/23/09
2/24/09
2/25/09

2/27/09
2/28/09

3/27/09
3/28/09

4/18/09
4/19/09
4/20/09

5/15/09
5/16/09

5/19/09
5/20/09

5/25/09
5/26/09

6/29/09
6/30/09
6/6/08
6/7/08
6/8/08
6/9/08

3/1/09
3/2/09
3/3/09
3/4/09
3/5/09
3/6/09

6/1/09
6/2/09

7/1/09

Figure 4. The variations of concentration and acid buffering capacity of PM10 and TSP during three stages.
 JOURNAL OF THE AIR & WASTE MANAGEMENT ASSOCIATION
concentration was the highest on the day before a
rainy day (June 1, 2009). The PM concentration
increased again after the rain event. There was a good
correlation between the PM10 and TSP, with
a correlation coefficient of 0.98. The average concentra-
tions of the TSP and PM10 were 191 μg/m3 and 155 μg/
m3, respectively. Approximately 81.2% of the TSP was
PM10, indicating that the washout of TSP by rain
mainly affected PM10 (Zhang et al. 2018).
Variation of chemical compositions of particulates
The differences among the chemical compositions of
PM during the three stages indicated that rainwater
appeared to have different scavenging effects on each
ion (Figures 5 and 6), the percentage change in con-
centration of PM samples and their components was
given in the supplementary file. Generally, the percen-
tage change in concentration of PM10 and TSP were
negative on average, that of most ions in TSP and in
PM10 also were negative, except for F− and Cl− in PM10
were positive on average which was likely due to the
scavenging effect of rain on PM were mainly on larger
size and large quantities of ions (Figure S1, Roy et al.
2019; Xu et al. 2017), indicating the possible scavenging
effect of rain on PM and the components. Table 2
shows a seasonal comparison of the PM chemistry
between rainy days and non-rainy days in the environ-
mental receptor, giving the differences in ionic compo-
sitions of the TSP and PM10. PM10-R and TSP-R
represent the PM on rainy days, and PM10-NR and
TSP-NR represent the PM on non-rainy days.
As shown in Table 2, the concentrations of the TSP
and PM10 were generally higher on non-rainy days than
on rainy days, and the seasonal dropping rates of the
TSP and PM10 were 23.6–60.9% and 30.2–56.6%,
respectively. The concentrations of SNA (sulfate,
nitrate, and ammonium) and other cations on non-
rainy days were generally higher than those on rainy
days in both PM10 and TSP most of the time. Unlike
SNA, the relative difference between the concentrations
of F− and Cl− during rainy days and non-rainy days
changed with the season.
Ca2+ and Mg2+ showed a similar tendency to that of
the PM concentration in both TSP and PM10. The
seasonal average dropping rates of Ca2+ were
37.2–73.0% and 39.2–71.6% in TSP and PM10, respec-
tively, and those of Mg2+ were 10.3–54.8% and
−9.0–63.9%. However, there were also several cases of
increasing, especially when the amount of rainfall was
relatively small. The concentrations of Ca2+ and Mg2+
during rainy days were mostly lower than those during
the other two stages, and the concentrations continually
decreased on consecutive rainy days most of the time.
1459
The concentrations of Ca2+ and Mg2+ on June 8th,
2008, and March 4th and 28th, 2009, increased com-
pared to those on the preceding days, and this was
because the amount of rainfall was relatively small
during these 3 days. The similar variation trends of
the Ca2+ and Mg2+ concentrations during the three
stages indicated their similar physical characteristics
(Gorham, Martin, and Litzau 1984; Likens and
Bormann 1974).
The temporal variation of the other two major
cations, Na+ and K+, in the particulates during the
campaign were in accordance with the overall trend of
Ca2+ and Mg2+ – their concentrations on rainy days
were lower than those on non-rainy days except for K+
and Mg2+ in the TSP (Table 2). The seasonal average
dropping rates of Na+ were 0.4–32.7% and 12.9–46.8%
in the TSP and PM10. For K+, the rates were
−20.5–73.4% and −9.7–71.8% in the TSP and PM10,
indicating that rain showed a certain scouring effect
on Na+ and K+ in PM. For NH4+, the ranges of the
dropping rates were 8.3–74.4% and 16.3–73.3% in the
TSP and PM10, respectively. The concentration of NH4+
in the TSP (5.9 ± 3.8 μg/m3) was lower than that in
the PM10 (8.1 ± 3.5 μg/m3) on non-rainy days, and the
same was true on rainy days, at 3.5 ± 1.7 μg/m3 in the
TSP and 5.2 ± 2.0 μg/m3 in the PM10. Both results
suggested that NH4+ was mostly enriched in the
PM10. The possible reason for the lower amount of
NH4+ in the TSP than in the PM10 is that reactions of
NH4+ with other ions such as Cl− and NO3− produce
volatile NH4Cl and NH4NO3, respectively, which can
easily decompose into gaseous ammonia, especially
under the climate conditions of the Yangtze River
Delta region, with an annual average temperature
approximately 20℃ and a relative humidity of approxi-
mately 70% (Harrison and Pio 1983; Querol et al. 2001;
Wall, John, and Ondo 1988; Zhuang et al. 1999).
Gaseous ammonia is more likely to react with SO2
and NOx to form SNA as secondary PM sources that
mostly exist in smaller particulates (Liu et al. 2017; Shi
et al. 2014; Tian et al. 2016). The scavenging effects
exerted on NH4+ and SO42- by rain showed high con-
sistency in both the TSP and PM10, and the scavenging
effect on NO3− in PM10 also displayed high consistency
with those on NH4+ and SO42-, which supported the
secondary sources of SNA. The dropping rates of NO3−
were 51.1–73.6% and −27.7–71.1% in the TSP and
PM10, and those for SO42- were 13.0–64.0% and
11.6–59.5%, suggesting that rain also played an impor-
tant role in the removal of these two anions (Tang et al.
2005).
Even through there were some occasions when the ion
concentrations increased after a rain event, overall, the
 1460

SO 4 2- NO3- Cl- F- NH 4 + Ca 2+ Mg 2+ K+ Na +
(µg/m³) (µg/m³) (µg/m³) (µg/m³) (µg/m³) (µg/m³) (µg/m³) (µg/m³) (µg/m³)

20
40
60
80

0
20
40
60

0
0
2
4
20
40

0
2
4
0
10

0.1
0.2
20
40
60
80
20
40

0
0
0
6/6/08
6/7/08
6/8/08
6/9/08
6/10/08
Y. HAN ET AL.

6/11/08
6/12/08
6/13/08
6/14/08

6/16/08
6/17/08
6/18/08
6/19/08

6/23/08
6/24/08
6/25/08
6/26/08
6/27/08
6/28/08

2/15/09

Figure 5. Variations of chemical compositions in PM10.

2/16/09

2/21/09
PM10

2/22/09
2/23/09
2/24/09
2/25/09

2/27/09
2/28/09
3/1/09
3/2/09
3/3/09
3/4/09
3/5/09
3/6/09

3/27/09
3/28/09

4/18/09
4/19/09
4/20/09

5/15/09
5/16/09

5/19/09
5/20/09

5/25/09
5/26/09

6/1/09
6/2/09

6/29/09
Rainfall(mm)

6/30/09
7/1/09

0
0
0
0
0
0

0
0
0

50
50
50
50
50
50

50
50
50
 SO 42- NO3- Cl- F- NH 4 + Ca 2+ Mg 2+ K+ Na +
(µg/m³) (µg/m³) (µg/m³) (µg/m³) (µg/m³) (µg/m³) (µg/m³) (µg/m³) (µg/m³)

20
40
60
0.2
0.4

0
20
40

0
1
2
0
0
0
1
2
0
5

20
40
10
20
10

0
0
0
5
6/6/08
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6/8/08
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6/10/08
6/11/08
6/12/08
6/13/08
6/14/08

6/16/08
6/17/08
6/18/08
6/19/08

6/23/08
6/24/08
6/25/08
6/26/08
6/27/08

Figure 6. Variations of chemical compositions in TSP.

6/28/08

9/12/08
9/13/08

2/15/09
2/16/09
TSP

2/21/09
2/22/09
2/23/09

2/27/09
2/28/09
3/1/09
3/2/09
3/3/09
3/4/09
3/5/09
3/6/09

3/27/09
3/28/09

5/19/09
5/20/09

5/25/09
5/26/09

6/1/09
6/2/09
JOURNAL OF THE AIR & WASTE MANAGEMENT ASSOCIATION

6/29/09
6/30/09
Rainfall(mm)

7/1/09

0
0
0
0
0
0

0
0
0

50
50
50
50
50
50

50
50
50
1461
1462 Y. HAN ET AL.

Table 2. Seasonal average concentration of TSP and PM10 and the chemical data during non-rainy days (-NR) and rainy days (-R) (μg/m3).*.
Season Num. TSP Na+ NH4+ K+ Mg2+ Ca2+ F− Cl− NO3− SO42-
Spring-NR 12 265.39 1.67 4.85 1.31 0.69 26.04 0.15 0.72 12.97 24.54
Spring-R 10 138.66 1.12 3.84 1.58 0.39 7.06 0.05 0.33 5.50 21.35
Summer-NR 12 142.00 0.29 4.23 0.85 0.39 4.32 0.08 0.14 1.43 18.91
Summer-R 11 108.55 0.28 3.88 0.83 0.35 2.71 0.08 0.15 0.70 14.91
Winter-NR 8 245.30 1.69 9.01 3.14 0.61 8.98 0.19 1.66 24.70 42.45
Winter-R 9 106.38 1.47 2.41 0.89 0.28 2.55 0.03 0.49 7.15 17.20
Season Num. PM10 Na+ NH4+ K+ Mg2+ Ca2+ F− Cl− NO3− SO42-
Spring-NR 13 190.20 1.66 11.38 2.22 1.05 9.31 0.07 0.39 14.28 32.49
Spring-R 11 132.72 0.88 9.53 2.43 0.38 4.24 0.02 0.38 4.56 28.73
Summer-NR 12 165.11 0.33 7.14 1.19 0.44 3.66 0.05 0.09 1.09 26.05
Summer-R 11 94.88 0.27 5.11 0.85 0.48 2.23 0.07 0.14 1.39 14.74
Winter-NR 8 130.94 1.26 9.37 1.72 0.14 1.83 0.02 0.49 11.21 43.24
Winter-R 9 118.70 3.10 3.52 1.46 0.60 3.46 0.05 0.88 7.90 29.72
Notes. *autumn is absent due to the number of PM samples is too little (2 R and 2 NR days).

above results indicated the generally synchronized scaven-
ging effect on PM chemical components exerted by rain.
Variation of the acid buffering capacity
The acid buffering capacity (A value) of PM decreased
with rain occurrence because the alkaline components in
the PM were washed out by rain (González and
Aristizábal 2012). The average dropping rates of the
A value for the TSP and PM10 were 30.6 ± 17.6% and
33.8 ± 16.0%, respectively. As shown in Figure 4, during
consecutive rain events, the A value fell gradually over
time. The possible reason for this phenomenon was that
the PM concentration decreased due to rain, especially
affecting the alkaline components (Larssen and
Carmichael 2000), as did its acid buffering capacity.
The potential cause of the more significant scouring
effect on alkaline than acidic components exerted by
rain is their different size distributions. Alkaline compo-
nents were found primarily in large particulates, and
acidic components are typically present in smaller parti-
culates (Blanco-Becerra et al., 2015; Barnard, Stensland,
and Gatz 1986; Samara and Tsitouridou 2000; Zhang
et al. 2018; Zheng et al. 1998). Generally, the PM10 and
TSP showed good consistency in terms of the acid buf-
fering capacity, with a correlation coefficient of 0.79
under the significance level of less than 0.001.
However, there also existed particulates that exhibited
the opposite behavior of the A value during rain events
between the PM10 and TSP, despite the similar variations
of their chemical compositions, and the reasons for this
effect need to be further studied. The average acid buf-
fering capacities of the PM10 and TSP were 1.31 ± 0.45
and 1.61 ± 0.84 ml/mg (consuming 131 ± 45 and 161 ±
84 nmol H+ per mg PM), respectively, indicating that the
local atmospheric PM had certain an acid buffering
capacity toward rain and that the TSP possessed
a higher A value than did the PM10. The acid buffering
capacity of airborne particulates at northern sites, such
as Beijing, which has an acid buffering capacity of 552.22
nmolH+/mgPM, was much higher than that at southern
sites, such as Wuyishan (−63.33 nmolH+/mgPM) (Ren
et al. 2011). Hangzhou is located at an intermediate
position between Beijing and Wuyishan and had
a moderate acid buffering capacity.
Correlation of the chemical compositions of PM and
rainwater
To investigate the effect of PM on the rainwater
chemistry, correlation analysis of the chemical compo-
sitions (nine ions) of PM collected during rainy days
with the ions in rainwater was conducted. It was
hypothesized that a strong correlation between PM
and rainwater chemistry represented a strong effect
on rainwater exerted by PM. On the contrary, the
impact was small. The correlation coefficient (R) of
the chemical compositions between rainwater and the
PM10 and TSP are listed in Table 3. The calculated
results were statistically significant (p ≤ 0.01) at the
95% confidence level, except for NO3−.
The Ca2+ in rainwater and PM was most strongly
correlated, and the correlation coefficient of PM10 was
greater than that of TSP, indicating that the PM10
during rainy day had a more significant effect on the
Ca2+ in rainwater than did the TSP. Na+ also displayed
a good correlation between rainwater and particulates,

Table 3. Correlation coefficient among soluble ions present in rainwater and PM in Hangzhou.
EC Ca2+ Mg2+ Na+ K+ NH4+ SO42- NO3− Cl− F−
PM10 m
0.507** 0.728** 0.381 0.464 0.486* 0.370 0.562** 0.385 0.398* −0.457*
TSPn 0.369* 0.554** 0.033 0.692** 0.290 0.165 0.506** 0.182 0.591** −0.741**
Notes. Number of PM10 during rainy day m = 30, number of TSP during rainy day n = 28.
*Represent the significance level of p ≤ 0.05, ** represent the significance level of p ≤ 0.01.
 JOURNAL OF THE AIR & WASTE MANAGEMENT ASSOCIATION 1463

suggesting that a large portion of the Na+ in rainwater Table 4. Enrichment factors for rainwater components relative
was from PM. The correlations of K+ and Mg2+ were to the seawater.
relatively worse than those of Na+ and Ca2+. NH4+ also K+/Na+ Mg2+/Na+ Ca2+/Na+ Cl−/Na+ SO42-/Na+
Seawater 0.02 0.23 0.04 1.16 0.12
had weak correlations, as the NH4+ in rainwater was Spring 4.75 0.47 22.58 0.53 19.06
likely from other sources such as the absorption of NH3 Summer 51.22 3.92 226.83 2.67 242.07
Autumn 35.64 1.12 124.75 1.99 103.71
by rain (Huo et al. 2012; Kumar, Yadav, and Kumar Winter 34.40 6.57 184.40 2.08 66.60
2014). For anions, Cl− showed a good correlation, Annual 25.00 1.48 101.18 1.47 96.23
similar to that of Na+, which was perhaps due to shar-
ing common marine sources (Tang et al. 2005) and
having similar transport patterns in the atmosphere area together with water vapor. The annual average EF
since the East China Sea is approximately 130 km values of Mg2+ and Cl− were very close to 1, indicating
away from the sampling site. In the TSP and PM10, F− that major sources of these two ions were sea salt. The
always exhibited a negative correlation with the corre- EF values of Ca2+ and SO42- were approximately 100,
sponding rainwater, indicating that F− in the rainwater suggesting that very little Ca2+ and SO42- came from sea
might be from other sources, such as rainout processes salt. The EF value of K+ was also far greater than 1,
in clouds, or gaseous pollutants, such as HF from cool- except for during spring; therefore, the proportion of
ants used in cooling systems, as well as from coal K+ from sea salt was very low most of the time.
burning, aluminum refinery, and phosphate fertilizer At the same time, principle component analysis
factories. There were two power plants to the north (PCA) was conducted using SPSS19.0. Table 5 shows
(12 km) and south (20 km) of the sampling site, respec- the varimax rotated principle component patterns of
tively. Typical industrial areas surrounded the sampling the rainwater compositions. Four PCs were extracted
site, so the power plants and industrial factories were from the rain samples, which explained about 75% of
potential sources of F− in the rainwater in Hangzhou. the variance. The communalities for all species were
NO3− showed a worse correlation between rainwater higher than 0.65, indicating that the four identified fac-
and particulates than did the other three anions, prob- tors were reasonable. Factor 1 had high loadings for K+,
ably because it mostly came from gaseous pollutants, Na+, Ca2+, and Mg2+ and accounted for about 31% of
such as NOX (Tian et al. 2016). For SO42-, the correla- the total variance. This factor was assumed to be asso-
tion coefficient of the PM10 was greater than that of the ciated with natural sources and the building industry,
TSP, suggesting that SO42- mainly originated from par- such as soil and road dust, cement plant emission and
ticulates emitted or formed during rainy days, espe- sea salt sources (Larssen and Carmichael 2000;
cially small particulates, such as secondary sulfate, Rodriguez et al. 2004). Factor 2 had high loadings for
which contributed a larger ratio in the PM10 than in NO3−, SO42-, and NH4+ and accounted for about 20% of
the TSP (Kavouras et al. 2013). the total variance. This factor was assumed to be asso-
ciated with secondary aerosol formation (Huo et al.
2012; Liu et al. 2017; Shi et al. 2014). The sampling site
Sources of chemical components in rainwater was surrounded by agricultural land and typical indus-
trial plants, so factor 2 represented the SNA chemical
To further determine the sources of the chemical spe-
components of rainwater, which were from NH3 (mainly
cies in rainwater, the enrichment factors of ions in
emitted from agricultural land), SO2 or sulfate (emitted
rainwater were calculated. Table 4 shows the enrich-
from power plants), NOX (emitted from motor vehicle
ment factors for the rainwater components relative to
those of seawater.
Generally, an EF value of near 1 represents that the Table 5. Principal component analysis of ionic compositions in
main contribution was from a reference source; other- Hangzhou rainwater from June 2008 to June 2009.
wise, the main contribution was related to other Variable Factor1 Factor 2 Factor 3 Factor 4 Communality
sources. The EF values of all ions were the lowest in H+ −0.278 0.105 0.826 0.016 0.770
F− 0.002 0.402 0.219 0.674 0.663
spring. According to the meteorological data from the Cl− 0.056 −0.221 −0.128 0.874 0.832
China Meteorological Administration, the predominant NO3− 0.048 0.851 −0.196 −0.185 0.799
SO42- −0.038 0.727 0.344 0.217 0.695
wind directions in Hangzhou during spring were east, K+ 0.879 −0.011 −1.227E-5 −0.151 0.796
and combined with the results of backward trajectory Na+ 0.773 −0.155 −0.214 −0.158 0.692
Ca2+ 0.831 0.152 0.008 0.215 0.760
analysis of air masses during the study period (which Mg2+ 0.867 0.027 0.248 0.244 0.873
can be found in the supplementary material), most time NH4+ 0.373 0.716 −0.047 −0.006 0.654
Eigenvalue 3.057 1.961 1.328 1.189
air masses would pass the marine area, so a large Variance % 30.567 19.608 13.278 11.887
amount of sea salt was transported from the marine Cumulative% 30.567 50.175 63.453 75.34
1464 Y. HAN ET AL.
emissions) and other industrial emissions. In factor 3,
there was a high loading for H+, but other ions showed
very low loadings, suggesting that the acidity of the
rainwater was influenced by multiple sources (Wang
et al. 2009). Factor 4 was likely associated with gaseous
pollutants, such as HF and HCl, and accounted for about
12% of the total variance. Although it had been sug-
gested that Cl− and Na+ were well correlated, the possi-
ble reason for Cl− and Na+ not being included in one
factor in the PCA analysis results was that the Cl− in
particulates is easily changed into gaseous forms, such as
HCl, especially in South China, with its high tempera-
tures, high humidity and strong radiation (Hsu et al.
2007). As mentioned before, the F− in rainwater was
mainly from coolant used in cooling systems such as
air conditioners and refrigerators and from coal burning,
aluminum refinery, and phosphate fertilizer factories
located in the surrounding environment.
Conclusion
There were severe acid rain and PM pollution problems
in the study area during the study period. The volume-
weighted mean pH of rainwater was only 4.44, and the
average concentrations of TSP and PM10 during the
study period were 191 μg/m3 and 155 μg/m3, respec-
tively. Both PM10 and TSP had certain acid buffering
capacities, with A values of 1.31 ± 0.45 and 1.61 ±
0.84 ml/mg, respectively. As China increases its efforts
to control particulate pollution, the acid rain problem
will probably become aggravated in some areas, which
needs to be considered at the same time.
The scavenging process of atmospheric particulate
matter appeared to be conducive to the mitigation of
acid rain pollution in areas in the Yangtze River Delta
region, such as Hangzhou. Rain appeared to have
a significant effect on the scavenging of particulate matter,
especially on the scouring of alkaline constituents. The
TSP changed concentration consistent with that of PM10,
and both the mass and chemical composition (soluble
ions) concentrations showed significant decreases during
most rainy days, and a continuous decrease occurred
when it continually rained for more than 1 day. When
rain stopped, the particulate concentrations increased
again. Overall, the acid buffering capacity of PM had
a similar change to that of the PM concentration during
the development of rain processes (three periods), as did
ions. The scavenging effect on particulates exerted by rain
had an important influence on the chemical compositions
of rain, except for F−, and was the main source of multiple
components in the rainwater. In spring, a large amount of
sea salt was transported from the marine area together
with water vapor, and sea salt was the major source
of Mg2+ and Cl− in rainwater. Sea salt contributed very
little Ca2+ and SO42-, and the proportion of K+ from sea
salt was very low except during spring. The principle
component analysis results suggested that the compo-
nents of the rain mainly derived from washout processes
acting on PM, such as crustal dust, building industry
sources (Ca2+), marine sources (Na+, Mg2+, K+ (in spring)
and Cl−) and anthropogenic sources, especially secondary
aerosols emitted from agricultural land, motor vehicles
and industrial plants (NO3−, SO42-, and NH4+). The F− in
the rainwater was mainly from coolants used in cooling
systems and from coal-burning and factories located in
the surrounding environment. This study can provide
data and theoretical support for the joint control of parti-
culate matter and acid rain pollution in both acid rain and
nonacid rain areas.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This study was supported by key projects in the science and
technology pillar program of Tianjin (09ZCGYSF02400).
About the authors
Yan Han and Hong Xu are Ph.D students of Nankai
University, College of Environmental Science and
Technology; The State Environment Protection Key
Laboratory of Urban Particulate Air Pollution and
Prevention in Tianjin, China.
Xiaohui Bi, Yufen Zhang, and Yinchang Feng are research
professors of Nankai University, College of Environmental
Science and Technology; The State Environment Protection
Key Laboratory of Urban Particulate Air Pollution and
Prevention, in Tianjin, China.
Fengmei Lin and Li Jiao are employees of The
Environmental Monitoring Center of Hangzhou in
Zhejiang, China.
ORCID
Yan Han http://orcid.org/0000-0003-1003-571X
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