Chemosphere 173 (2017) 318e325

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Physicochemical conditions and properties of particles in urban runoff

and rivers: Implications for runoff pollution
Qian Wang a, Qionghua Zhang a, b, *, Yaketon Wu a, Xiaochang C. Wang a, **
a
b

Key Lab of Northwest Water Resource, Environment and Ecology, MOE, Xian University of Architecture and Technology, Xian 710055, China
International Science & Technology Cooperation Center for Urban Alternative Water Resources Development, Xian 710055, China

h i g h l i g h t s

The physicochemical conditions varied greatly from rainwater to runoff, and to rivers.

Higher proportion of nano-scale particles was in runoff than in rivers.

The ratio of turbidity and TSS indicated the size and settleability of particles.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 28 June 2016
Received in revised form
4 January 2017
Accepted 12 January 2017
Available online 16 January 2017

In this study, to gain an improved understanding of the fate and fractionation of particle-bound pollutants, we evaluated the physicochemical conditions and the properties of particles in rainwater, urban
runoff, and rivers of Yixing, a city with a large drainage density in the Taihu Lake Basin, China. Road
runoff and river samples were collected during the wet and dry seasons in 2015 and 2016. There were
signicant differences between the physicochemical conditions (pH, oxidation-reduction potential (ORP),
and electroconductivity (EC)) of rainwater, runoff, and rivers. The lowest pH and highest ORP values of
rainwater provide the optimal conditions for leaching of particle-bound pollutants such as heavy metals.
The differences in the physicochemical conditions of the runoff and rivers may contribute to the
redistribution of pollutants between particulate and dissolved phases after runoff is discharged into
waterways. Runoff and river particles were mainly composed of silt and clay (<63 mm, 88.3%e90.7%), and
runoff particles contained a higher proportion of nano-scale particles (<1 mm) but a lower proportion of
submicron-scale particles (1e16 mm) than rivers. The ratio of turbidity to TSS increased with the proportion of ne particles and was associated with the accumulation of pollutants and settling ability of
particles, which shows that it can be used as an index when monitoring runoff pollution.
2017 Elsevier Ltd. All rights reserved.

Handling Editor: X. Cao

Keywords:
Physicochemical conditions
Particle characteristics
Fractionation
Urban runoff
Urban river

1. Introduction
Runoff volumes, runoff coefcients, and pollutant loads have
tended to increase in recent decades, as a result of the increases in
impervious surfaces caused by rapid rates of urbanization worldwide (Sun et al., 2015). Increases in these indexes exacerbate the
risk of urban oods. Therefore, drainage systems are generally
designed to ensure rapid discharge of runoff into adjacent

* Corresponding author. Key Lab of Northwest Water Resource, Environment and

Ecology, MOE, Xian University of Architecture and Technology, Xian 710055, China.
** Corresponding author.
E-mail addresses: qionghuazhang@126.com (Q. Zhang), xcwang@xauat.edu.cn
(X.C. Wang).
http://dx.doi.org/10.1016/j.chemosphere.2017.01.066
0045-6535/ 2017 Elsevier Ltd. All rights reserved.

waterways. It has been reported that more than 90% of runoff is

discharged directly into rivers in districts that have implemented
rain and sewage diversion. This means that the increasing number
of non-point source pollutants are more widely distributed, and are
difcult to control with centralized measures (Loperdo et al.,
2014).
Non-point source pollution, recognized as a pertinacious illness
of urban rivers because of its ongoing contribution to their pollution, has received considerable attention in previous studies
(Reidsma et al., 2012). The concentrations, loads, and rst ush
effects of runoff pollutants have been investigated, and rst ushes
of pollutants with high concentrations and loads have also been
observed during rainfall events (Kim and Sansalone, 2008; Chow
et al., 2013; Zhang et al., 2013; Chow and Yusop, 2014; Gasperi
et al., 2014). The processes that control the build-up and wash-off

Q. Wang et al. / Chemosphere 173 (2017) 318e325

of road-deposited sediment (RDS) have been explored to investigate the fate and fractionation of runoff pollutants, including their
accumulation, mobility, and fractionation (Sansalone and Ying,
2008; Joshi and Balasubramanian, 2010; Yuen et al., 2012).
Studies have shown that particle size plays an important role in the
accumulation and mobility of pollutants (Gunawardana et al., 2012;
Zhao and Li, 2013; Li et al., 2015). Also, pollutants tend to accumulate in ne particles that can be transported easily by rainfall
(Gunawardana et al., 2015; Zhao et al., 2016). Other studies have
reported that the fractionation of pollutants between the particulate and dissolved phases is determined by their binding states with
particles and the physicochemical conditions (pH, oxidationreduction potential (ORP) and electroconductivity (EC)) in the
water environment (Morselli et al., 2003; Duong and Lee, 2009;
Zhang et al., 2016). For example, water environments with low
pH, low ORP, and high ORP favor the release of heavy metals (HMs)
associated with carbonates, Fe and Mn oxides, and organic matter,
respectively (Sutherland et al., 2012; Maniquiz-Redillas and Kim,
2014). These studies provide valuable information about runoff
pollution and its control. However, little is known about the fate
and fractionation of pollutants contained in runoff once they are
discharged into waterways.
The fate and fractionation of runoff pollutants are closely related
to their potential impacts on waterways; dissolved pollutants are
directly bioavailable, while the sediments may clog waterway beds,
smother biota, damage the respiratory systems of organisms,
attenuate light, and act as vectors of hydrophobic pollutants
(Helmreich et al., 2010; Zuo et al., 2012; McKee and Gilbreath,
2015). Therefore, it is important to analyze the physicochemical
conditions and particle characteristics of the main receptors of RDS
during runoff events, namely rainwater, runoff, and waterways, to
evaluate the fate and fractionation of runoff pollutants. However,
previous studies have tended to examine the particle properties
and fractionation of particle-bound pollutants in runoff or rivers
separately, and have rarely considered the physicochemical conditions. Consequently, we have little appreciation of whether or
how the properties of particles in, and physicochemical conditions
of, rainwater, runoff, and rivers differ from each other, nor do we
have a good understanding of the potential fate of particle-bound
runoff pollutants once they are discharged into waterways. A
clearer understanding of these processes will facilitate improved
management of runoff pollution.
The objectives of this study therefore were to 1) detect the
differences in the physicochemical conditions and particle characteristics of rainwater, urban runoff, and rivers, and 2) analyze the
potential fate and fractionation of runoff pollutants during rainfall
events. We hope that the information produced will support
management of runoff pollution and contribute to the preservation
of urban waterways.

319

discharging runoff rapidly in most conditions. When runoff is

generated, untreated runoff ows directly into the nearest
waterways.
The catchment of the Nanhe River (blue lines in Fig. 1A), one of
the three largest rivers in the Taihu Basin, is to the west of Taihu
Lake. The rivers ow from west to east and ultimately feed into
Taihu Lake after traversing Xijiu, Tuanjiu, and Dongjiu Lakes and
other interconnected rivers (Fig. 1A and B). The water input to Taihu
Lake from the Nanhe River system accounts for around 25% of the
total inputs to the lake. Agriculture, aquaculture, forestry, and urban areas dominate land use in the Nanhe catchment. The central
urban area is in the middle reaches and comprises residential,
commercial, and industrial areas. River and runoff samples were
collected from August 2015 until May 2016. A total of 34 sampling
sites, comprising 3 stagnant rivers (blue triangles, Fig. 1B) and 31
owing rivers (red triangles, Fig. 1B), distributed throughout the
Nanhe system were monitored. We collected samples of urban
runoff from three road sites (green circles, Fig. 1B) in residential,
commercial, and industrial areas.
2.2. Sampling strategy
Six different types of samples, namely rainwater, urban runoff
(UR), stagnant rivers during the wet season (SR-W), stagnant rivers
during the dry season (SR-D), owing rivers during the wet season
(FR-W), and owing rivers during the dry season (FR-D), were
collected. Individual samples of local rainwater were collected in
clean polyethylene vessels in an open area. Runoff samples were
collected from the inlet grating at the roadside (Fig. 1C) at 5-min
intervals during ve rainfall events. The rainfall amounts, rainfall
durations, and antecedent dry periods ranged from 5.2 to 26.8 mm,
from 72 to 318 min, and from 23.8 to 359 h, respectively. We
collected surface water samples from the middle of the river
channels (Fig. 1D). River samples were collected once or twice a
month during the dry season when the number of antecedent dry
days ranged from 2 to 8 d. River samples were collected through
two rainfall events in the wet season at time intervals of 0.5, 1, 2, 4,
and 6 h. Samples were collected in pre-washed 1-L polyethylene
bottles. It should be noted that the sampling program was not
designed to identify the cause-and-effect linkages between urban
runoff and rivers, but to understand the physicochemical

2. Material and methods

2.1. Study area and sampling sites
We chose Yixing, a city in the Taihu Lake Basin in Eastern China,
as our study area. This city is characteristic of the area and, with its
extensive waterway network, has a large drainage density. Yixing
has a population of approximately 1.24 million and covers a total
area of 1996.6 km2, 16.8% of which is occupied by water bodies. The
urban area of 66.3 km2 is crisscrossed by rivers, with a river density
of up to 2.27 km km2. Yixing has a subtropical monsoon climate.
The average annual temperature, rainfall, number of rain days, and
evaporation are 15.7  C, 1177 mm, 136.6 d, and 849 mm, respectively. The drainage is via a rain and sewage diversion system that
comprises only main pipes or a few branch pipes that are capable of

Fig. 1. (A) Geographical position. The blue lines and red virtual frame represent the
Nanhe River system and the study area, respectively. (B) River sampling sites. The red
and blue triangles represent the sampling sites in the owing and stagnant rivers,
respectively. The green circles represent the road runoff sampling sites in the urban
area. (C) and (D) are photographs of runoff sampling and river sampling, respectively.
(For interpretation of the references to colour in this gure legend, the reader is
referred to the web version of this article.)

320

Q. Wang et al. / Chemosphere 173 (2017) 318e325

conditions and sediment properties. We collected and analyzed a

total of 246 river samples and 151 runoff samples.

analysis to t the settling curves. We used IBM SPSS statistics

version 19 (IBM Corporation, Armonk, NY, USA) for the statistical
analysis.

2.3. Samples analysis

3. Results
The physicochemical parameters, including pH, ORP, and EC,
were measured for rainwater, runoff and river samples either in situ
or in the laboratory as soon as possible after collection using a
multi-parameter analyzer (Hach HQ 40d) that was calibrated before
use. The particle characteristics, including turbidity, total suspended solids (TSS), organic matter content (OM), surface
morphology, size distribution, and settleability of particles, were
also determined.
2.3.1. Particle content and composition
Turbidity was measured using a laboratory turbidimeter (Hach
2100 N). Total suspended solids and OM were determined by the
gravimetric and loss-on-ignition methods, respectively.
As is already well known, TSS is an indicator of the mass of
suspended solids and turbidity characterizes the optical properties
of suspended solids. We might speculate therefore that ne particles contribute less to TSS because of their lower density and
contribute more to turbidity because of their large specic surface
areas that can effectively hinder light. In other words, turbidity and
TSS are indicators of particle size that cannot be expressed separately. Hence, the ratio of turbidity to TSS (Tur/TSS) can be used to
characterize the relative composition of particle sizes, such that a
higher Tur/TSS value indicates mainly ne particles and vice versa.
2.3.2. Morphological analysis
We carried out various sediment analyses to determine if the
Tur/TSS ratio could be used to characterize the relative composition
of particle sizes. First, we observed the surface morphology of
particles with a scanning electron microscope (Hitachi S-3400 N ,
Japan). We prepared dry solids of ve representative runoff samples, the Tur/TSS of which ranged from 0.35 to 1.74. We were not
able to analyze river particles for morphological properties because
the TSS concentrations were very low (median 37 mg L1), which
meant that it was very difcult to separate enough particles.
2.3.3. Particle size distribution (PSD)
We determined the PSD of runoff samples collected at runoff
times of between 0 and 260 min. The turbidities and TSS concentrations of these samples ranged from 41.6 to 728 NTU and from 70
to 1456 mg L1, respectively. We also determined the PSD for river
samples with turbidities and TSS concentrations that ranged from
24.4 to 159 NTU and from 29 to 207 mg L1, respectively. We used a
laser particle size analyzer for the PSD analysis (Mastersizer, 2000,
Malvern Instruments Ltd.).
2.3.4. Settleability
We used the precipitation method in the laboratory to investigate the settleability of runoff and river particles. Runoff or river
samples were poured into a specially designed settling column
with a volume of 15 L. The turbidity and TSS were measured on
samples collected from the middle of the column at time intervals
of 0.5, 1, 2, 4, 8, and 12 h. We analyzed six river samples and three
runoff samples.
2.4. Statistical analysis
Because the variables were not normally distributed, we used a
nonparametric test (independent-samples t-test) to detect signicant differences between the physicochemical and particle properties among the different sample types. We used regression

3.1. Differences in the physicochemical conditions

3.1.1. pH
The pH value reects the acidity of a solution. The pH of rainwater, urban runoff, and rivers ranged from 3.99 to 5.19, from 7.33
to 9.11, and from 6.99 to 8.16, respectively. The average pH
decreased in the following order: UR > SR-W > FR-W > FR-D > SRD > rainwater (Table 1). Nonparametric tests indicated that the pH
of urban runoff was signicantly higher than that of river samples.
Moreover, the pH of the stagnant rivers differed signicantly between the wet and dry seasons. Runoff discharges had more inuence on the pH of stagnant rivers than of owing rivers. The
acidity of the urban runoff and rivers was signicantly lower than
the acidity of the local rainwater.
3.1.2. ORP
ORP represents the overall oxidation-reduction potential of a
solution. A high positive value indicates a strong oxidizing ability. In
sedimentary geology, ORP ranges have been classied into 4
groups, so that 400e650 mV, 200e400 mV, 0e200 mV,
and 200e0 represent oxidation, weak oxidation, weak reduction,
and reduction, respectively (Guo and Jia, 2008). The ORP values of
rainwater, urban runoff, and rivers ranged from 242.5 to 376.7, from
157.2 to 245.9, and from 211.2 to 291.4 mV, respectively. In contrast
to pH, the ORP was lowest for urban runoff. The ORP of rainwater
and rivers indicated weak oxidation, while the ORP of urban runoff
extended from weak reduction to weak oxidation. The average ORP
decreased in the following order: rainwater > FR-D > SR-D > SRW > FR-W > UR (Table 1). Results from nonparametric tests indicated that the ORP values for both stagnant and owing rivers were
signicantly higher than the values for urban runoff. The ORP
values for owing rivers differed signicantly during the wet and
dry seasons. Runoff discharge had more inuence on the ORP of
owing rivers than of stagnant rivers. The ORP of both urban runoff
and rivers was signicantly lower than that of local rainwater.
3.1.3. EC
Electroconductivity is associated with the salinity, ion concentrations and impurity of a solution. Low EC values indicate pure
water. The EC of rainwater, urban runoff, and rivers ranged from
27.7 to 70.8, from 46.3 to 506.0, and from 153.4 to 656 ms cm1,
respectively. The average EC was ranked as follows: FR-D > FRW > SR-D > SR-W > UR > rainwater (Table 1). Nonparametric tests
indicated that the EC values of UR, SR-W, SR-D, FR-W, and FR-W
were signicantly different. Runoff discharges caused obvious decreases in the EC of urban rivers. The EC of the rivers was signicantly higher than the EC of local rainwater. However, while the EC
values of runoff were higher than those of rainwater, the differences were hard to dene because of the large variations in runoff.
3.2. Particle characteristics of urban runoff and rivers
3.2.1. Particle content and composition
Road deposited sediment and associated pollutants are partly
washed off and transported to waterways as runoff particles. The
turbidity of urban runoff and rivers ranged from 10.1 to 746 and
from 4.2 to 201 NTU, respectively. The average turbidity values
were ranked as follows: UR > FR-W > SR-W > FR-D > SR-D
(Table 1). Runoff discharges caused the turbidity of the stagnant

Q. Wang et al. / Chemosphere 173 (2017) 318e325

321

Table 1
Physicochemical properties of rainwater, runoff, and rivers in Yixing, China.
Parameters

Sample type
SR-W

pH
ORP (mV)
EC (ms cm1)
Turbidity (NTU)
TSS (mg L1)
OM (%)

SR-D
a

FR-W
b

7.56 0.34
258.0 21.3ab
454.7 49.5b
12.2 5.2b
15.7 8.8b
56.3 20.1a

7.87 0.14
251.9 12.9a
249.1 86.2a
44.7 28.6a
95.1 77.0a
34.1 12.5ab

FR-D
bc

7.74 0.09
250.2 17.1a
455.6 117.2bc
49.4 27.5a
72.2 58.5a
27.7 7.6b

UR
b

7.70 0.11
263.8 8.1b
614.4 20.9d
41.2 30.8a
51.7 39.7c
22.5 13.2a

Rainwater
d

8.42 0.43
190.9 20.1c
131.4 107.1e
129.3 118.5c
267.3 236.5a
29.8 10.4b

4.49 0.50e
342.9 56.9d
52.4 15.8e
/
/
/

The superscript characters ae demonstrated the results of nonparametric tests, and different characters indicated that there was signicant difference existed.

rivers to increase signicantly. The TSS of urban runoff and rivers

ranged from 16 to 1728 and from 6 to 259 mg L1, respectively. The
average TSS was ranked as follows: UR > SR-W > FR-W > FRD > SR-D (Table 1). Runoff discharges caused the TSS of both
owing and stagnant rivers to increase signicantly. Furthermore,
the OM was highest for SR-D and lowest for FR-D, but there were
no other differences. Runoff particles make a signicant contribution to the impairment of waterways, and should be studied in
more detail.
The Tur/TSS plotted with the TSS concentrations (Fig. 2A and B)
varied considerably for both runoff and rivers, and ranged from
0.24 to 1.91 and from 0.39 to 3.82, respectively. The values of the
Tur/TSS ratio were noticeably different for runoff and rivers. Values
of the Tur/TSS ratio were uniformly low for runoff when TSS concentrations were higher than 500 mg L1 (Fig. 2A) but there was no
trend when TSS concentrations were less than 500 mg L1. This
may be attributed to the TSS source, which was determined by the
quantity of particles stored on the road surface, the kinetic energy
of rainfall, and other factors such as the RDS load, rainfall intensity,
runoff time, and antecedent dry days (Wijesiri et al., 2015; Zhao
et al., 2016). Since less energy is needed to remove ne particles
from the road surface, runoff with higher Tur/TSS values is possibly
generated under low rainfall intensities while runoff with lower

2.0

1.5
1.0

Tur/TSS

.5
0.0
0

500

1000

1500

2000

3
2
1
0
0

60

120

180

240

TSS (mg/L)
Fig. 2. Relationship between Tur/TSS and TSS concentrations for runoff (A) and rivers
(B).

Tur/TSS values is generated under high rainfall intensities. Nevertheless, there was a clear declining trend for rivers (Fig. 2B). The
Tur/TSS values were around one under most conditions (78%), and
some extreme values were found when the TSS concentrations
were lower than 50 mg L1, which again may be attributed to the
TSS source. Rivers with higher TSS concentrations contain more
sediment and sediment particles that are larger, derived from the
shipping disturbances, that make more of a contribution to TSS
than to turbidity. However, particles in rivers with lower TSS concentrations tend to be ner, and make less of a contribution to TSS
than to turbidity.
3.2.2. Morphology of particle surfaces
To validate the relationship between Tur/TSS and particle size,
particles in runoff samples with Tur/TSS ratios ranging from 0.35 to
1.74 were separated and dried to facilitate examination of the
surface morphology (Fig. 3AeC). The majority of particles were
irregularly shaped and had variable dimensions. As we expected,
the particle size decreased as the Tur/TSS increased. For example,
the Tur/TSS ratio of C3 was signicantly higher than that of the
other samples and many nano-scale particles were visible in the
SEM micrograph; also, there were more micron- and submicronscale particles in samples with lower Tur/TSS values. This shows
that the Tur/TSS ratio can be used to characterize the relative
composition of the particle sizes.
3.2.3. Particle size distribution (PSD)
In sedimentary geology, particles with diameters <4, between 4
and 63, 63 and 125, 125 and 250, 250 and 500, and 500 and 1000
are classied as silt, clay, very ne sand, ne sand, medium sand,
and coarse sand, respectively (Zhao et al., 2010). We differentiated
the particle sizes of sediments in runoff and rivers into these seven
fractions (Table 2). Runoff and river sediments were mainly
comprising silt and clay (<63 mm), which accounted for
90.7 12.5% and 88.3 9.2% of their total volumes, respectively.
The clay fraction dominated (4e63 mm), and accounted for
67.1 6.8% and 76.6 14.1% of the sediment particles in rivers and
runoff, respectively. Furthermore, the proportion of <4 mm particles
in rivers was nearly twice the corresponding proportion in runoff,
indicating that rivers transported ner particles. Nano- and
submicron-scale particles were the main contributors to the differences in PSD between runoff and rivers. Previous studies have
shown that pollutant concentrations may be one order of magnitude higher in nano-scale (<0.3 mm and 0.3e1 mm) particles than in
submicron- and micron-scale particles (Fedotov et al., 2014).
Because particles <16 mm are acknowledged to be closely associated with decreases in water clarity, we carried out further comparisons of the <16 mm particles (Table 2). The proportions of
<16 mm particles in different runoff and river samples varied
considerably and ranged from 22.8% to 86.7% and from 45.0% to
83.5%, respectively, with averages of 59.4 17.4% and 69.1 10.8%,
respectively. The proportion of <16 mm particles was slightly higher

322

Q. Wang et al. / Chemosphere 173 (2017) 318e325

A Tur/TSS=0.35

B Tur/TSS=0.48

C2 Tur/TSS=1.03

C1 Tur/TSS=0.90

C3 Tur/TSS=1.74

Fig. 3. SEM micrographs of runoff particles with different Tur/SS values. The magnications were 6000  , 8000  , and 10000  for groups A, B, and C, respectively.

Table 2
The PSD of urban runoff and rivers in Yixing, China.
Ranges (mm)

Rivers %

Urban runoff %

<4
4e63
63e125
125e250
250e500
500e1000
Nano- and submicron-scale
<1
1e4
4e10
10e16

21.2 8.7
67.1 6.8
5.7 4.3
2.1 2.1
3.9 3.0
/

14.1 8.5
76.6 14.1
6.2 8.1
2.4 4.4
0.6 0.9
0 0.1

2.1 2.2
20.1 6.2
32.5 4.1
20.3 5.1

2.4 2.4
11.7 6.7
25.0 16.1
14.5 2.2

in rivers than in runoff, because of the higher proportion of

submicron-scale (1e4, 4e10, and 10e16 mm) particles. It is worth
noting that there were more nano-scale (<1 mm) particles in runoff
than in rivers. These very ne particles should receive more
attention because of their high pollutant concentrations, mobility,
and bioavailability.
3.2.4. Settleability
The variations in turbidity with settling time are illustrated in
Fig. 4. The settling of runoff and river particles were a good t for
the exponential distribution. Goodness of t values ranged from
0.743 to 0.977, which indicates that the settling speed gradually
decreased with time (Zhao et al., 2010; Kayhanian et al., 2012). This
is because larger and denser particles settled rapidly and smaller
and lighter particles settled more slowly. The Tur/TSS also
increased as the settling time increased (not shown in the paper).
The settling process can be divided into two stages: the initial
period with rapid settling and a steady period with homogeneous
settling. The runoff particles settled more rapidly than the river
particles in the initial period, but they settled at comparable speeds
in the steady period. This result was somewhat expected because
runoff particles are generally denser than river particles. Moreover,
river samples with lower turbidity tted better than samples with
higher turbidity, whereas there was no trend between the tting
and turbidity of runoff samples. The better t was attributed to the
homogeneous composition of the particle sizes. As discussed in

section 3.2, the particle sizes of river samples with low turbidity
were more homogeneous than those with high turbidity. However,
rainfall intensity rather than turbidity determined the particle size
composition of runoff samples. Therefore, it was the particle
composition that actually determined the settling process, and the
settleability of samples with lower Tur/TSS values was better
despite their weaker tting.

4. Discussion
4.1. The fate and fractionation of runoff pollutants
The pollutants associated with particles in different binding
states can leach into aqueous phases from particle surfaces under
specic pH, ORP, or EC conditions (Kartal et al., 2006). As shown in
Table 3, HMs are usually partitioned into four fractions by the
modied BCR three step sequential extraction procedure, namely
acid extractable (F1), reducible (F2), oxidizable (F3), and residual
(F4) fractions that associate with carbonates, Fe and Mn oxides,
organic matter, and minerals, respectively (Bacon et al., 2006). The
rst three fractions (F1F2F3) comprise the mobile part and may
be released to the aqueous phase through desorption or dissolution
(Zhang and Wang, 2009). As mentioned by various researchers, the
F1 fraction is sensitive to low pH, the F2 fraction is sensitive to
either low pH or low ORP, while the F3 fraction is sensitive to high
ORP values (Li et al., 2013).
Acid rain (with a pH of 3.99e5.19) in the present study provides conditions that are conducive to the release of the F1 and F2
fractions. The signicantly higher pH of urban runoff indicates that
the acidity of the rainwater was neutralized by the alkalinity
provided by RDS (Huber et al., 2016). Although the pH of the rivers
increased slightly following runoff discharges, the near-neutral
environment did not facilitate the release of particle-bound pollutants. The ORP values of rainwater, runoff, and rivers were
within the weak reduction and weak oxidation categories. When
the wash-off commences, there is leaching of the F3 fraction of
RDS pollutants because of the high oxidizing ability of rainwater,
and the ORP in runoff subsequently decreases. The slight increase
in the ORP of rivers after receiving runoff may further enhance the
release of the F3 fraction. Furthermore, the EC increased from

Q. Wang et al. / Chemosphere 173 (2017) 318e325

200

250
initial period

steady period

initial period

steady period

160

200
UR(222 NTU) R2=0.856
UR(84.5 NTU) R2=0.929
UR(66.1 NTU) R2=0.743

150

Turbidity (NTU)

Turbidity (NTU)

323

100

FR (160 NTU)
FR (136 NTU)
FR (59.4 NTU)
FR (47 NTU)

120

R2=0.896
R2=0.884
R2=0.940
R2=0.977

80

40

50

0
0

30

60

90

120

150

180

30

60

90

Time (h)

120

150

180

Time(h)

Fig. 4. Variations in turbidity with settling time for runoff (A) and river (B) samples.

Table 3
The characteristics of different fractions of HMs.
Items

Fractions
F1 (acid extractable)

F2 (reducible)

F3 (oxidizable)

F4 (residual)

Binding state
Sensitive to environment
Proportion (%)

Carbonates
Low pH
0.7e24.7
0e58.5
8.7e54.7

Fe and Mn oxides
Low pH, low ORP
3.4e59.0
7.8e85.4
22.8e65.5

Organic matter
High ORP
11.1e67.8
5.2e63.0
3.8e24.5

Minerals
/
1.6e62.2
5.6e25.6
10.1e38.7

Cu
Pb
Zn

The proportion of Cu, Pb, Zn in different fractions are obtained from Oahu, Hawaii, US; Hangzhou and Nanjing, China; Kayseri, Turkey; Nerima city, Tokyo; Dresden, Germany.

rainwater, to runoff, and then to rivers, indicating the increasingly

complicated physical, chemical, and biological transformations of
pollutants. The TSS of runoff was approximately 5e17 times higher
than that of rivers, most of which contributed to the river sediments. Because of the variations between the runoff and river
environments, pollutants will inevitably be redistributed between
the particulate and dissolved phases by physical, chemical, and
biological processes.
Worldwide, there is considerable variation in the physicochemical conditions of rainwater, runoff, and rivers. Previous
studies have reported pH values ranging from 3.77 to 7.12, from
4.15 to 9.11, and from 6.95 to 9.25; ORP values ranging from 166 to
376.7 mV, from 157.2 to 245.9 mV, and from 211.2 to 291.4 mV, and
EC values ranging from 3.9 to 70.8 ms cm1, from 24.1 to
2670 ms cm1, and from 153.4 to 1713 ms cm1 in rainwater, runoff,
and rivers, respectively (McQueen et al., 2010; Yang et al., 2013;
Zhang et al., 2013; Xu et al., 2015; Mimura et al., 2016; Morillas
et al., 2016; Zhao et al., 2017; Zheng et al., 2017). The differences
may be attributed to the inuence of anthropogenic activities,
such as emissions of acid aerosols (mainly SOx and NOx) or
wastewater from industrial and trafc-related activities (Ouyang
et al., 2015; Morillas et al., 2016). Furthermore, the fractions of
Cu, Pb, and Zn concentrations in urban RDS (Table 3) from six
cities worldwide varied greatly in all the fractions of a given metal,
which may be related to the source of RDS and the associated HMs
(Zhang and Wang, 2009; Sutherland et al., 2012; Kumar et al.,
2013; Li et al., 2013; Maniquiz-Redillas and Kim, 2014; Zhang
et al., 2015). The fractionation of pollutants will therefore vary
considerably from site-to-site because of variations in the physicochemical properties of rainwater, runoff, and rivers, and the
binding states of pollutants.

4.2. Implications for runoff pollution control

It is generally accepted that urban runoff with high pollutant
concentrations or loads is under control. However, the potential
risk from runoff is determined by the bioavailability of pollutants
rather than the total mass (Zhang et al., 2016). Because of the
importance of ne particles in the accumulation and mobility of
particle-bound pollutants, it is more bioavailable for particles with
ne sizes. Therefore, particle size must be considered when controlling runoff. The PSD results indicate that both river and runoff
particles were mainly comprising the <63 mm fraction (88.3%e
90.7%), and a considerable proportion of the particles were <10 mm
(39.1%e54.7%). Heavy metals are mainly concentrated in nanoscale (<1 mm) particles, and <16 mm particles are acknowledged
to be closely associated with the degradation of water clarity, so
more attention should be paid to nano- and submicron-scale particles in RDS and runoff, and runoff control measures should be
designed accordingly (Fedotov et al., 2014).
Most runoff particles in Yixing were <125 mm (96.9%), which is
comparable with the results from other studies (89.5%e95.0%) (F. T.
Wakida et al., 2013; Zhao and Li, 2013). Hence, RDS particles in this
size category are more likely to be washed from the surface during
rainfall. Runoff pollution derives from the transport of mobile RDS
(<125 mm) and the leaching of immobile RDS retained on the road
surface. Therefore, the implementation of, and improvements in,
road sweeping will help to prevent the leaching of dissolved pollutants from coarse RDS.
We found that Tur/TSS was an effective indicator of the relative
composition of particle sizes. Many researchers have reported that
pollutants are concentrated in ne particles, so it might be expected that runoff with a high Tur/TSS value has higher pollutant

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Q. Wang et al. / Chemosphere 173 (2017) 318e325

concentrations. Furthermore, the general occurrence of runoff with

high Tur/TSS ratios under low rainfall intensities implies that runoff
with these properties comprises only a small part of total runoff.
Hence, even though the volume is small, runoff with high Tur/TSS
values should be controlled because of the extremely high
pollutant concentrations. Further, the relationship between Tur/TSS
and the settleability of particles indicates that the settleability of
runoff with higher Tur/TSS was weaker than runoff with lower Tur/
TSS. Hence, the Tur/TSS ratio can also be used to set appropriate and
optimal hydraulic retention times (HRT) in runoff control measures
that involve presettling processes to achieve most effectiveness
(Maniquiz-Redillas et al., 2014).
5. Conclusion
We evaluated the physicochemical conditions (pH, ORP, and EC)
and particle characteristics (turbidity, TSS, size distributions, and
settleability of particles) that governed the fate and fractionation of
particle-bound pollutants in rainwater, urban runoff, and rivers.
The results show that the physicochemical properties (pH, ORP, EC)
of urban runoff, rivers, and rainwater differed signicantly. The low
pH and high ORP in rainwater were conducive to the leaching of
particle-bound pollutants. Different environments and the more
sophisticated physical, chemical, and biological processes in rivers
may contribute to the redistribution of pollutants between the
particulate and dissolved phases after runoff is discharged into
waterways. Both runoff and river particles were predominantly
composed of silt and clay (<63 mm), most of which were within the
nano- and submicron-scale (<16 mm) categories. There should be
concern about the higher proportion of nano-scale (<1 mm) particles in runoff because of their high pollutant concentrations,
mobility, and bioavailability. The ratio of turbidity to TSS (Tur/TSS),
as an indicator of the relative composition of particle sizes, was
associated with the accumulation of pollutants and the settleability
of particles, and so could contribute to assessments of the effectiveness of runoff pollution control measures.
Acknowledgements
This study is supported by the National Natural Science Foundation of China (Grant No.51508447), the National Program of
Water Pollution Control in China (Grant No. 2014ZX07305-002),
and Program for Innovative Research Team in Shaanxi (PIRT) (Grant
No. 2013KCT-13).
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