Download as pdf or txt
Download as pdf or txt
You are on page 1of 13

Environ Earth Sci (2016) 75:1105

DOI 10.1007/s12665-016-5902-0

THEMATIC ISSUE

Assessment of heavy metal contamination in water body


and riverbed sediments of the Yanghe River in the Bohai Sea,
China
Cuiping Kuang1 • Yunchi Shan2 • Jie Gu3 • Haibing Shao4 • Wanlei Zhang5 •

Yongfeng Zhang5 • Jiabo Zhang6 • Huixin Liu6

Received: 5 February 2016 / Accepted: 18 July 2016 / Published online: 25 July 2016
Ó Springer-Verlag Berlin Heidelberg 2016

Abstract Several famous beach bathing places and aqui- analysis (CA) and principal component analysis (PCA). The
culture areas locate in the Yanghe River coast of the Bohai results of heavy metal contamination in riverbed sediments
Sea, which are very sensitive to the quality of water and showed that: (1) the mean PLI in the range of 1.0–1.1
sediment from river discharges. To assess heavy metal indicated a progressive deterioration, and the Igeo revealed
contamination, heavy metal in water body and riverbed the pollution in the order of Cd [ Cu [ Zn [ Pb [ Cr; (2)
sediments was investigated in the flood and dry seasons in the RI presented that the pollution in the downstream was
2013 at 8 sites along the Yanghe River. All heavy metal much higher than that in the upstream; (3) the contamina-
concentrations in water body were very low and less than tion decreased in the upstream due to decreased domestic
the threshold value of drinking water quality standard of wastewater where far from the development zone Funing
China. There was no significant correlation between heavy Town, while it increased in the downstream because of
metal pollution in water body and riverbed sediments. dense population and tourists in the coastal zone; and (4) the
Sediment pollution was assessed by five approaches PCA and FA demonstrate that domestic sewage was a major
including pollution load index (PLI), geo-accumulation source of heavy metal contamination.
index (Igeo), potential ecological risk index (RI), cluster
Keywords Heavy metal  Pollution indices  Riverbed
sediments  Contamination assessment  The Yanghe River
This article is part of a Topical Collection in Environmental Earth
Sciences on ‘‘Environment and Health in China II’’ guest edited by
Tian-Xiang Yue, Cui Chen, Bing Xu and Olaf Kolditz.
Introduction
& Cuiping Kuang
cpkuang@tongji.edu.cn
With the rapid growth of population, urbanization and
& Jie Gu industrialization, various contaminants enter the surface
jgu@shou.edu.cn
water system (Onodera et al. 2008). Rivers, therefore, have
1
College of Civil Engineering, Tongji University, been subjected to increasing stress as the end point of the
Shanghai 200092, China wastewater from the adjacent area (Phiri et al. 2005). In
2
East China Electric Power Design Institute Co., LTD, aquatic system, heavy metal contamination has received
Shanghai 200063, China considerable concern due to its toxicity, abundance, per-
3
College of Marine Sciences, Shanghai Ocean University, sistence and bio-accumulation (Sin et al. 2001; Barlas et al.
Shanghai 201306, China 2005). Heavy metal enters into rivers through atmospheric
4
Helmholtz Centre for Environmental Research (UFZ), deposition, sewage, urban wastewater and agricultural and
Permoserstr. 15, 04103 Leipzig, Germany industrial runoff (Cheng et al. 2013). While transported by
5
Marine Environmental Monitoring Center of Hebei Province, the river stream, heavy metal can easily be absorbed by
Qinhuangdao 066002, China sediments and deposit on the riverbed, so they are dis-
6
Qinhuangdao Mineral Resource and Hydrogeological tributed between the aqueous phase and sediments (Sin
Brigade, Qinhuangdao, Hebei, China et al. 2001). In the estuarine, a large quantity of heavy metal

123
1105 Page 2 of 13 Environ Earth Sci (2016) 75:1105

contamination can be found inside the sediments and only a Methodology


small portion stays dissolved in water (Gaur et al. 2005).
Heavy metal may accumulate in human bodies and Study area
result in health problems (Cook et al. 1990). Heavy metal
also poses threat to the coastal and marine environment The Yanghe River, with a drainage basin of approximately
when riverine flow and sediments discharged into sea. Due 1100 km2, is the longest river (100 km) in Qinhuangdao
to the water discharge fluctuations and low residence time (Hebei Province Department of Land and Resources 2007).
of sediments in the water, only measuring the pollutants in In the upper stream, there are two main tributaries named
the water body is not conclusive (Varol 2011), and heavy the East Yanghe River and the West Yanghe River that
metal concentrations in the riverbed sediments must also be merge into the Yanghe Reservoir (see Fig. 1). The East
considered for assessment quality of whole river system. Yanghe River origins the Qinglong County and has a
Sediments act as the main carriers of heavy metal and the catchment area 306 km2 surrounded by mountainous areas
potential secondary sources of pollution in the river system that result in main pollutants into the river from water loss
(Segura et al. 2006). Under changing physical and chemi- and soil erosion due to heavy rain in the flood season. In
cal conditions, heavy metal in the bed sediments may recent years, the East Yanghe River is almost dry in most
reenter the water column via sediment resuspension or of times except for the flood season. The West Yanghe
desorption (Dong et al. 2012). And heavy metal concen- River originates from the Lulong County with a catchment
trations in sediments change spatially and temporally, area 343 km2, where is densely population area and is rich
which are very important in clarifying the pollution history in sweet potato that leads to a lot of starch processing
(Morillo et al. 2004). So the analysis of heavy metal in plants. Large pollution from domestic sewage and indus-
riverbed sediments is essential to study heavy metal pol- trial wastewater is discharged into the West Yanghe River
lution and assessment river system quality. Heavy metal and finally into the Yanghe Reservoir.
interacts with many surrounding environmental factors; The Yanghe Reservoir locates in Funing County, which
especially in estuaries due to tidal current and saline water was built and put into use in 1961. The reservoir has a
intrusion, many physical and chemical processes are dif- drainage basin of 755 km2, i.e., 68.6 % of whole Yanghe
ferent from those in the river environment with freshwater basin area. The reservoir design standard is a one in
moving in one direction (Ip et al. 2007). Investigation on 100-year flood with a corresponding design flood level at
heavy metal from either natural or anthropogenic sources is 62.4 m and reservoir storage volume of 2.75 9 108 m3. The
beneficial to comprehensively evaluate their impacts on the reservoir check standard is a one in 1000-year flood with a
ecosystem. corresponding design flood level at 65.32 m and reservoir
The City of Qinhuangdao, located in the northeast of storage volume of 3.53 9 108 m3. The normal storage water
Hebei Province, is an important coastal city in the north of level is 57 m, and the reservoir storage volume is
China. Several rivers flow through the city and finally 1.47 9 108 m3. The design discharge capacity of reservoir
discharge into the Bohai Sea. The Yanghe River, with a flood discharging tunnel is 206 m3/s with a maximum value
total length of about 100 km and a catchment area of about of 500 m3/s. The main function of the reservoir is for urban
1100 km2 (Hebei Province Department of Land and water supply, and other functions are flood control, irriga-
Resources 2007), is the longest among all local rivers in tion and generating electricity (Li et al. 2010; Shao et al.
Qinhuangdao. With the rapid population growth and 1999; Zhang et al. 2010). Generally, water quality in the
industrial development, the river water quality deteriorated, reservoir is good with most of water quality index less than
and the Yanghe River was one of the major pollution- grade II standard value, such as chemical oxygen demand
emitting outlets in Hebei Province (Liu et al. 2011a). (COD) with a value in the range of 2.1–4.9 mg/L (Wang
Several coastal beach bathing places and aquiculture areas and Zheng 2013; Zhang et al. 2010), which is much better
located near the Yanghe River estuary, heavy metal pol- than water quality at the reservoir downstream. The con-
lution in the river raised concerns among the public, and centrations of heavy metal Cu and Cr in the surface sedi-
the potential risk to coastal and marine environment needs ment of the reservoir were 26.1–44.1 and 42.7–56.8 mg/kg,
to be investigated (Kuang et al. 2010; Liu et al. 2011b). respectively (Cai et al. 2007).
The objectives of this study are (i) to evaluate the level We focus our study on the lower river course of the
of heavy metal contamination in water body and riverbed Yanghe Reservoir, i.e., from the reservoir outlet in the west
sediments of the Yanghe River, (ii) to present the spatial to the river mouth in the east, with a length of about 40 km,
and temporal distribution of heavy metals in the river and as shown in Fig. 1. The study area locates in an extrat-
(iii) to identify natural and anthropogenic sources of heavy ropical monsoon climatic region, the annual mean tem-
metal contamination in study area. perature is about 10 °C, and rainfall is 750 mm, varying

123
Environ Earth Sci (2016) 75:1105 Page 3 of 13 1105

Study area

Fig. 1 Location of the study area

temporally in summer and winter (Cui and Li 2006). The Sample collection
multi-year averaged runoff of the Yanghe River is
2.48 9 108 m3, and the Yanghe Reservoir inflow is The water and riverbed sediment samples were collected in
1.84 9 108 m3. Normally, the runoff in July to September August (i.e., the flood season) and November (i.e., the dry
is about 73.5 % of annual runoff. A large number of vil- season) of 2013. Figure 1 shows the locations of eight
lages and towns are built on both sides of the river, sampling, namely S1–S8 along the river from the upstream
including the Funing Town, the center of the Funing to the river mouth. S1 in the upstream is seated in the
County. The river receives domestic raw sewage water, northwest of Funing Town, which is about 10 km down
agricultural runoff and also industrial wastewater from the from the Yanghe Reservoir. S4 and S5 are situated the area
surrounding areas, which have caused the deterioration of near some traffic arteries such as railways, the national
the river ecosystem. Due to the fact that water quality in the road and the coastal highway. S8 in the river downstream is
Yanghe Reservoir is much better than that in the reservoir near the river mouth. The distance between adjacent sites is
downstream, flood discharge from the reservoir in the flood 3–4 km. Salinity, pH and suspended solids (SS) were
season can improve water quality of the reservoir down- measured on sites by using salinometer, pH meter and
stream (Hu 2016). portable turbidimeter, respectively. Unfiltered water sam-
The Yanghe River flows into the Bohai Sea to be affected ples were collected from flowing water body at the center
by tides. The tidal movement in Bohai Sea experiences a of the river at 8 sites and kept in acid-cleaned polypropy-
tidal wave system of the North Yellow Sea entering from lene bottles for the analysis of heavy metal and chemical
Bohai Strait. The tidal waves in Bohai Sea can be divided oxygen demand (COD). The top 20 cm riverbed sediments
into two separate tidal wave systems: the north branch and were taken by using a clamshell-type sampler at the same
the west branch. The north branch moves northward, locations and were sealed in pre-cleaned polyethylene
passing Liaodong Bay and presenting a clockwise rotation bags. All samples were then placed in a cooler and trans-
with Qinhuangdao as its center, while the west branch ported to the laboratory immediately for further analysis.
moves westward, passing Bohai Bay and exhibiting a
counterclockwise rotation with the mouth of the Yellow Chemical analysis
River as its center (Pan et al. 2014). The mouth of the
Yanghe River is located between the two branches near the First, sediment samples were air-dried. Pebbles and plant
amphidromic point, experiencing a regular diurnal tide with fragments were removed. Then, they were digested with
a low tidal range of 0.74 m and low tidal flow velocities less the automatic digestion apparatus (AtuoDigiBlock S60)
than 0.2 m/s in SW-NE directions in the coastal water. and stored in acid-rinsed polyethylene bottles. Polarization

123
1105 Page 4 of 13 Environ Earth Sci (2016) 75:1105

spectrometer for heavy metal was applied for the mea- P


where X ¼ 1n ni¼1 Xi is the mean of X and Y is the mean of
surement of Cu, Zn, Pb and Cd. In addition, the concen- Y. The correlation coefficient rXY ranges from -1 to 1. A
tration of Cr was analyzed using a flame atomic absorption correlation coefficient close to 1 indicates a positive rela-
spectrophotometer (FAAS). COD was measured with the tionship between X and Y, while a correlation coefficient close
basic potassium permanganate method. All analytical steps to -1 indicates a negative relationship. A correlation close to
were under strict quality control according to the standard 0 indicates the absence of relationship between X and Y.
procedure (State Environment Protection Agency 2004;
The Yangtze Water Environment Monitoring Center 2013). Contamination factor (CF) of Heavy Metal and Pollution
Deionized water was used throughout the experiments. The Load Index (PLI)
glassware was washed with dilute acid followed by several
portions to distilled water. The CF is the ratio obtained by dividing the concentration
Paralleled examination was used in the chemical anal- of each metal in the sediment samples by background
ysis, all experiments were carried out in triplicate, and the value:
measured concentrations were within a ±3 % error limit.
The original data used in the study were the mean value of Cheavy metal
CF ¼ ð2Þ
paralleled examinations. Cbackground
CF values were interpreted and suggested by Hakanson
Assessment of contamination (1980), where CF \ 1 means low contamination;
1 \ CF \ 3 indicates moderate contamination;
Approaches such as the Pearson correlation coefficients, 3 \ CF \ 6 is considerable contamination; and CF [ 6
enrichment factor (EF), contamination factor (CF), pollution suggests very high contamination.
load index (PLI), geo-accumulation index (Igeo) and poten- The PLI is defined as the nth root of the multiplications
tial ecological risk index (RI) have already been successfully of the concentrations (CFmetals) (Suresh et al. 2011):
applied to assess the impact of heavy metal in sediments (Qi
et al. 2010; Varol 2011; Hou et al. 2013). Furthermore, to PLI ¼ ðCF1  CF2  CF3      CFn Þ1=n ð3Þ
obtain meaningful results in complex data sets, multivariate where CF is the contamination factor and n is the number
chemometric techniques are adopted. Principal component of metal species. The PLI gives an assessment of the
analysis (PCA), factor analysis (FA) and cluster analysis overall toxicity status for each sample, and it also shows
(CA) have also become good approaches in environmental the contribution of each metal to the pollution. PLI value of
study, especially for heavy metal analysis (Fu et al. 2014; one is a threshold, i.e., if PLI \ 1, there is no heavy metal
Yuan et al. 2014). On the interpretation of geochemical data, pollution; otherwise, when PLI [ 1, it means that a pol-
the choice of background values plays an important role. The lution exists (Varol 2011), which indicates progressive
average shale values or the average crustal abundance data deterioration of sediment quality.
were often used as reference baselines (Loska and Wiechula
2003; Pekey 2006; Yuan et al. 2014). However, the average Geo-accumulation index (Igeo)
shale value in China is different with other countries, the
national background shale value usually adopted (Chen and Geo-accumulation index has been used since 1960s (Müller
Liu 1992; Liu et al. 2009), which is also adopted in this 1969). It is defined by the following equation:
study. Several different methods (as described below) were  
used to assess the heavy metal pollution level in water body Cn
Igeo ¼ Log2 ð4Þ
and riverbed sediments to better understand the quality of 1:5Bn
the Yanghe River. where Cn is the concentration of metal examined in sedi-
ment samples and Bn is the geochemical background con-
Pearson correlation coefficients centration of the metal (n). The factor 1.5 is the background
matrix correction factor due to lithospheric effects. The
The Pearson correlation coefficient is a measure of asso- geo-accumulation index consists of seven grades as shown
ciation between two random variables. It explores the lin- in Table 1.
ear relationship between two quantities X and Y, each with
n individuals: Potential ecological risk index (RI)
X n
Xi  X Yi  Y
rXY ¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Pn ffi  qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Pn ð1Þ The RI was first introduced by Hakanson (1980), and its
2 2
i¼1 ðXi  XÞ i¼1 ðYi  YÞ
i¼1
value can be calculated by the following formulas:

123
Environ Earth Sci (2016) 75:1105 Page 5 of 13 1105

Table 1 Indices and grades of geo-accumulation index


Class 0 Class 1 Class 2 Class 3 Class 4 Class 5 Class 6

Igeo Igeo \ 0 0 B Igeo \ 1 1 B Igeo \ 2 2 B Igeo \ 3 3 B Igeo \ 4 4 B Igeo \ 5 Igeo C 5


Pollution Practically Unpolluted to Moderately Moderately to Heavily Heavily to Extremely
Grade unpolluted moderately polluted polluted heavily polluted polluted extremely polluted
polluted

Cfi ¼ CDi =CRi ð5Þ independent variables. It extracts the eigenvalues and
eigenvectors from the covariance matrix of original vari-
Eri ¼ Tri  Cfi ð6Þ ables and summarizes the statistical correlation among
X
m constituents in water with a minimum loss of original
RI ¼ Eri ð7Þ information (Zhao et al. 2012). Principal components (PCs)
i¼1 are extracted by using PCA, while a PC is a linear com-
where Cfi is the contamination coefficient; CDi is the present bination of observable variables.
concentration of heavy metals in sediments; CRi is the pre- Factor analysis further reduces the contribution of less
industrial record of heavy metal concentration in sedi- significant variables obtained from PCA, and the new
group of variables, known as varifactors (VFs), are
ments; Eri is the potential risk of individual heavy metal; Tri
extracted through rotating the axis defined by PCA (Singh
is the toxic-response factor for a given heavy metal; and RI
et al. 2004). A VF may include unobservable and hypo-
is the sum of potential risk of heavy metal.
thetically latent variables.
Cluster analysis (CA)

Cluster analysis is a multivariate statistical method used to


Results
classify the objects of the system into categories or clusters
Five pollution indices of heavy metals in water and sedi-
based on their nearness or similarity (Varol and Sen 2009).
ment, namely Zn, Cu, Pb, Cr and Cd, were selected, which
Hierarchical clustering is the most common approach,
were the most polluted metals in the Yanghe River. The
where clusters are formed sequentially by starting with the
other metals such as Fe, Hg and As were relatively in very
most similar pair of objects and forming higher clusters in a
low level in the river and were not measured.
step-by-step fashion (Varol and Sen 2012). The Euclidean
distance usually gives similarities between two samples,
Heavy metal contamination in water body
and it can be calculated as:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Xn
The results of heavy metal concentrations in water samples
dij ¼ ðxik  xjk Þ2 ð8Þ
of the Yanghe River are shown in Table 2. The average
k¼1
concentration of heavy metal in water body followed a
where dij is the distance between samples, n is the number decreasing order of Zn [ Cu [ Pb [ Cr [ Cd. The aver-
of samples and x is the sample of every cluster. CA was age concentrations of Cu and Zn were higher in August
often performed on the normalized data by Ward’s method (2.26 and 9.03 lg/L) than those in November (1.26 and
(Ward 1963), which analyzes variance approach to evalu- 8.38 lg/L). However, the average concentrations of Cd, Pb
ate the distances between clusters. It minimizes the sum of and Cr were lower in August (0.07, 0.89 and 0.21 lg/L,
distances of two arbitrary clusters that can be formed at respectively) than those in November (0.10, 1.31 and
each step until all the clusters formed into one. CA has 0.43 lg/L, respectively). The lower concentration of heavy
been proven to be a powerful grouping mechanism metal might be due to the dilution of high river discharge,
(Simeonov et al. 2000; Panda et al. 2006). and the higher concentration of Cu and Zn might be due to
the increased domestic sewage and industrial runoff
Principal component analysis (PCA) and factor analysis entering the river in August. The maximum concentration
(FA) of all heavy metal in both wet season and dry seasons did
not exceed the threshold value required by the drinking
PCA is a pattern recognition technique that attempts to water standard of China.
interpret the variance within a large set of intercorrelated In order to establish relationships between heavy metal
variables by converting them into a smaller set of in water body with physical and chemical properties such

123
1105 Page 6 of 13 Environ Earth Sci (2016) 75:1105

Table 2 Concentrations of
Metal Cu Zn Cd Pb Cr
heavy metals in water body
(lg/L) Aug. Nov. Aug. Nov. Aug. Nov. Aug. Nov. Aug. Nov.

Max 3.73 1.91 18.8 12.9 0.1 0.15 1.83 1.76 0.25 0.51
Min 1.28 1.05 5.16 4.1 0.04 0.04 0.59 1.02 0.14 0.32
Mean 2.26 1.26 9.03 8.38 0.07 0.10 0.89 1.31 0.21 0.43

Table 3 Pearson correlation


Cuw Znw Cdw Pbw Crw pH SAL COD SS
matrix in water body
Cuw 1
Znw -0.405 1
Cdw -0.306 -0.011 1
Pbw -0.482 0.506a 0.620a 1
Crw -0.552a -0.194 0.353 0.364 1
pH -0.071 -0.066 0.472 0.204 0.261 1
SAL -0.140 -0.033 0.310 0.130 0.046 0.165 1
COD 0.415 0.137 -0.259 -0.277 20.622a 0.053 0.173 1
SS -0.261 0.204 0.423 0.697b 0.569a 0.284 -0.254 -0.370 1
Bold values represent correlation with significance, superscripts a and b represent significance at the 0.05
and 0.01 probability level, respectively, and subscript w represents heavy metal in water body

Table 4 Comparison of concentrations of heavy metal in riverbed sediments in the Yanghe River and other documented data from Fu et al.
(2014) (mg/kg dw)
Metal Yanghe River River and Lakes in China River and Lakes in the world
Aug. Nov.
Mean Range Mean Range Mean Range Mean Range

Cu 29.1 14.2–48.7 21.7 10.5–31.6 91 1.3–924.5 191.1 0.8–5075.6


Zn 96.9 42.3–184 51.7 19.5–80.9 194.1 23.3–1250.5 388.7 3.9–8286.3
Cd 0.19 0.02–0.64 0.13 0.05–0.25 3 0.02–81.79 0.94 0.0–25.9
Pb 22 10.8–34.4 19.8 14.1–28.4 90.5 1.7–513.7 137.3 0.0–5778.1
Cr 33.4 12.6–93.5 55.1 26.1–95.7 76.6 2.7–229.6 51.51 0.0–234.6

as pH, salinity (SAL in Table 3), SS and COD, Pearson Table 4 shows the comparison of heavy metal concen-
correlation matrices were calculated and are shown in trations in the riverbed sediments in the Yanghe River
Table 3. It implies that SS has a significant correlation with with some reported data in other rivers in China and in
Pb (r = 0.697, p \ 0.01) and Cr (r = 0.569, p \ 0.05), the world (Fu et al. 2014). It presents that the concen-
COD has a close relation with Cr (r = -0.622, p \ 0.05), tration of Cu, Zn, Pb, Cr in other rivers in China is 2–4
while pH and SAL have no correlation with heavy metal in times higher than those in the Yanghe River, and Cd is
water body. about 20 times higher. When compared with rivers and
lakes in other countries in the world, the heavy metal
Heavy metal contamination in riverbed sediment concentrations of Cu, Zn, Pb are much lower (i.e., 1/6–2/
3) in the Yanghe River.
The concentration ranges of heavy metal in riverbed Table 5 shows the correlation of heavy metal in water
sediments were as follows: Cu, 10.5–48.7; Zn, 19.5–184; body and in riverbed sediments. Cu in riverbed sediments
Cd, 0.02–0.64; Pb, 10.8–34.4; and Cr, 12.6–95.7 mg/ shows a significant correlation with Zn (r = 0.599,
kg dw. The average concentration of heavy metal was in p \ 0.05) and Cr (r = -0.528, p \ 0.05) in water body,
the descending order of Zn [ Cr [ Cu [ Pb [ Cd. Zn in riverbed sediments has a significant correlation with

123
Environ Earth Sci (2016) 75:1105 Page 7 of 13 1105

Table 5 Person correlation


Cuw Znw Cdw Pbw Crw Cus Zns Cds Pbs Crs
matrix between heavy metal in
water body and riverbed Cuw 1
sediments
Znw -0.405 1
Cdw -0.306 -0.011 1
Pbw -0.482 0.506a 0.620a 1
a
Crw 20.552 -0.194 0.353 0.364 1
a
Cus 0.173 0.599 0.100 0.207 20.528a 1
a
Zns 0.521 -0.291 -0.247 20.551 20.612a 0.265 1
Cds 0.320 -0.316 -0.242 -0.466 -0.267 0.110 0.851b 1
Pbs 0.003 0.427 0.261 0.225 -0.225 0.742b -0.077 -0.177 1
Crs -0.154 -0.150 0.416 0.218 0.416 0.066 -0.090 -0.051 -0.112 1
Subscript s represents heavy metal in riverbed sediments, others are defined as the same in Table 3

Table 6 CF and PLI values of


Site CF values PLI
heavy metal in riverbed
sediments Cu Zn Cd Pb Cr
Aug. Nov. Aug. Nov. Aug. Nov. Aug. Nov. Aug. Nov. Aug. Nov.

S1 2.44 1.37 0.96 1.08 0.48 1.84 1.35 0.92 0.42 1.11 0.91 1.23
S2 1.71 0.81 0.85 0.72 0.47 1.46 1.46 0.72 0.54 0.84 0.88 0.88
S3 1.41 0.52 0.62 0.29 0.32 0.77 0.97 0.62 0.65 0.57 0.71 0.53
S4 0.71 1.58 0.94 0.61 1.39 3.57 0.46 1.20 0.23 0.96 0.63 1.32
S5 1.07 1.42 1.67 1.19 2.87 3.16 0.89 1.13 0.30 1.23 1.07 1.49
S6 1.52 0.68 2.25 0.54 5.74 1.19 1.04 0.61 0.36 0.48 1.49 0.66
S7 1.37 0.97 1.44 0.90 1.42 1.66 0.74 0.92 1.73 1.21 1.29 1.10
S8 1.42 1.33 2.72 0.77 9.07 1.71 0.54 0.60 0.72 1.78 1.68 1.13
Mean 1.46 1.09 1.43 0.76 2.72 1.92 0.93 0.84 0.62 1.02 1.08 1.04

Pb (r = -0.551, p \ 0.05) and Cr (r = -0.612, p \ 0.05) Indices of heavy metal contamination in riverbed
in water body. It is also found that Pb in riverbed sediments sediments
has a positive correlation with Zn and Cd in water body,
implying that they may be from a common source. All The results of heavy metal contamination factors (CFs) and
these present the same heavy metal does not have an pollution load index (PLI) are presented in Table 6. The CF
obvious correlation in water body and riverbed sediments, values were in the descending order of Cd [ Cu [
which indicates that heavy metal in water body is not from Zn [ Pb [ Cr in August and Cd [ Cu [ Cr [ Pb [ Zn in
the natural source of contaminants release from riverbed November. The highest CF value was 9.07 for Cd at Site 8
sediments, i.e., the anthropogenic discharge of pollutants in August, and the lowest was 0.23 for Cr at Site 4 in
may be the main source. August. Cd had the highest CF value on average, which is
categorized as a ‘‘moderate contamination.’’ The CF values
for Cd showed ‘‘considerable contamination’’ at Site 4 and
Discussion Site 5. The CF values for Cd indicated ‘‘considerable
contamination’’ and ‘‘very high contamination’’ at Site 6
Due to no obvious correlation in water body and riverbed and Site 8, respectively. The CF values for heavy metal
sediments and very low concentration of heavy metal in were below 3 at other sites, which suggest that the heavy
water body, the detailed discussions were made on the metal in riverbed sediments had low or moderate contam-
heavy metals in riverbed sediments. Different methods ination. Total contamination factors of heavy metal in
were used to assess heavy metal contaminations in riverbed riverbed sediments followed the order of S8 [ S5 [ S6 [
sediments, the spatial and temporal concentration varia- S7 [ S1 [ S4 [ S2 [ S3.
tions of heavy metals were analyzed, and the sources of The PLI values ranged from 0.53 to 1.68 for heavy metal
heavy metals were identified. in riverbed sediments and followed the order of

123
1105 Page 8 of 13 Environ Earth Sci (2016) 75:1105

Fig. 3 Pollution load index (PLI) value of heavy metal in riverbed


Fig. 2 Geo-accumulation index (Igeo) value of heavy metal in sediments
riverbed sediments

S8 [ S5 [ S7 [ S6 [ S1 [ S4 [ S2 [ S3. The PLI val- river in two seasons (Fig. 4). The decreasing trends of RI
ues at Site 2 and Site 3 were below 1 in two seasons, values were similar as those of PLI values in both flood and
indicating no heavy metal pollution in riverbed sediments. dry seasons. The RI value was the highest and Cd
Other sites, PLI values between 1 and 2, indicated that accounted for 67.6 % of the RI value at Site 8 in August. In
pollution existed. The mean PLI values of 1.08 and 1.04 in general, the percentage of each heavy metal for the RI at all
the wet and dry seasons, respectively, showed a progressive sites was Cu: 8.4–35.6 %, Zn: 2.8–5.7 %, Cd: 7.0–67.6 %,
deterioration of the riverbed sediments. Pb: 4.9–33.7 %, Cr: 10.3–56.7 % in August and Cu:
Figure 2 presents geo-accumulation index (Igeo) of 15.1–39.2 %, Zn: 1.4–3.0 %, Cd: 19.9–39.3 %, Pb:
heavy metal in riverbed sediments. The Igeo values 8.5–21.0 %, Cr: 29.4–57.5 % in November, respectively. It
decreased in the order of Cd [ Cu [ Zn [ Pb [ Cr. The is found that Zn had a rather low ecological risk, while Cd
range of Igeo values for Cu and Zn were -1.70 to 0.52 and and Cr posed a relatively high potential ecological risk.
-2.51 to 0.73, respectively, indicating unpolluted to Furthermore, the ecological risk of Cr was higher in
moderated pollutions in riverbed sediments. Cd had the November than that in August.
highest Igeo values, with a range from -2.70 to 2.13, which Based on the RI values of heavy metal in riverbed
means that the riverbed sediments in unpolluted to heavily sediment samples, cluster analysis (CA) was applied to
polluted, whereas the Igeo values of Pb and Cr were below group the similar sampling sites and different heavy metals
0, suggesting no pollution in riverbed sediments. as shown in Figs. 5 and 6, respectively. The 8 sampling
sites were grouped into four clusters at (Dlink/Dmax) 9
Spatial and temporal variation of heavy metal 100 % \ 20 %, where Dlink and Dmax are the link and max
in riverbed sediments distance between clusters, respectively. Cluster 1 (S8) was
located near the river mouth, where flow velocity decreased
Concentrations of heavy metal in riverbed sediments varied and heavy metal accumulated in riverbed sediment. Cluster
along the river in different seasons. As shown in Fig. 3, 2 (S6), located in the downstream of the river, also suffered
concentrations of heavy metal at Sites 5, 6, 7 and 8 located relatively high pollution. Cluster 3 (S4, S5) was in the
in the downstream of the river were much higher than those middle of the river, and the potential risk of heavy metal
at Sites 1, 2, 3 and 4 in the upstream of the river. Most of changed dramatically in the two seasons (Fig. 4). Cluster 4
the PLI values of heavy metal in the downstream were consisted of S1, S2, S3 and S7, and the potential risk of
more than 1, indicating heavy metal pollution. On the other heavy metal changed little in the two seasons (Fig. 4). S1,
hand, majority of PLI values in the upstream were below 1, S2 and S3 located in the upstream of the river, which were
which means no heavy metal pollution. The PLI values lightly polluted. CA was performed on the heavy metal data
followed the decreasing trends of S8 [ S6 [ S7 [ S5 [ set and group the five heavy metals into three clusters at
S1 [ S2 [ S3 [ S4 in August and S5 [ S4 [ S1 [ S8 [ (Dlink/Dmax) 9 100 % \ 10 %. Cluster 1 (Cd) corre-
S7 [ S2 [ S6 [ S3 in November. sponded to high potential risk, and cluster 2 (Zn) corre-
Potential ecological risk index (RI) was used to study sponded to low potential risk. Cluster 3 contained Cu, Pb
the potential risk of five kinds of heavy metal along the and Cr, which might be from the same source.

123
Environ Earth Sci (2016) 75:1105 Page 9 of 13 1105

Fig. 4 Potential ecological risk index (RI) value of heavy metal in riverbed sediments in different seasons. a flood season in August and b dry
season in November

Fig. 5 Hierarchical dendrogram for riverbed sediment sampling sites

In general, heavy metal concentrations in riverbed Fig. 6 Hierarchical dendrogram for heavy metal in riverbed
sediments varied differently in August and in November, sediments
and the pollution in the downstream was much higher than
that in the upstream of the study area. In the upstream of Source identification
the river, the concentration of metal got lower when the
site moves further from the Funing development zone The approaches of PCA and FA were applied to further
(Funing County). The potential risks of S4 and S5 clus- identify sources of heavy metal. PCA of the entire data set
tered in one group showed different variation trend in both (all heavy metal concentrations in riverbed sediments)
flood and dry seasons (see Figs. 4, 5). Furthermore, in the shown in Table 7 revealed three PCs with eigenvalues [ 1
downstream of the river, the closer to the estuary the site which explained about 93.7 % of the total variance in the
was, the higher level of heavy metal contamination was data set. The first PC accounting for 38.8 % of the total
found. variance was correlated (loading [ 0.70) with Zn and Cd.

123
1105 Page 10 of 13 Environ Earth Sci (2016) 75:1105

Table 7 Rotated component matrix for heavy metal elements in


sediments
Element Component
1 2 3

Cu 0.201 0.932 0.108


Zn 0.961 0.088 -0.046
Cd 0.958 -0.060 -0.013
Pb -0.168 0.934 -0.128
Cr -0.047 -0.013 0.996
Eigenvalue 1.937 1.732 1.018
% of variance explained 38.747 34.647 20.352
% of cumulative 38.747 73.394 93.746
PCA loadings [ 0.7 are shown in bold

The second PC accounting for 34.7 % of the total variance


was correlated with Pb and Cu. And the third PC Fig. 7 PCA results for riverbed sediment sampling sites
accounting for 20.4 % of the total variance was correlated
with Cr. or rainfall. Except a small number of approved pesticides
These PCs were subjected to varimax rotation and contain, other heavy metals, Cu and Zn, are the extensively
generated VFs. Three VFs explained about 93.7 % of the used elements for pesticides in China (Luo et al. 2009).
total variance. The relations among these heavy metals Trace metal such as Cu and Zn are also presented in
based on the three components are illustrated in three-di- livestock diets, the amount of which may be increased with
mensional (3D) space (Fig. 7). The heavy metals assemble the feed additives in the countryside. And the content of
into 3 groups. Pb and Cu are clustered in one major group, trace metal elements in animal manures consequently
indicating that they have similar patterns and sources. Zn increased with the use of the feed additives (Fan et al.
and Cd are included in the second group. Cr is far away 2013). So the heavy metals in livestock manures also pose
from the other heavy metals, implying a unique source. a potential threat to the river environment.
Generally, Cu is used in car lubricants and Pb is used in Figure 8 shows the main regional distributions in two
leaded gasoline (Fu et al. 2014). The Yanghe basin is a sides of the Yanghe River. In Funing County, COD dis-
tourism place and an important transportation area con- charging from animal industry, paper industry, farming
necting the south and the north of China, which is crossed industry and metal industry was 9073t, 4197t, 295t and 133
by traffic arteries such as railways, the national road and t, respectively, in 2012 (Hebei Development and Reform
the coastal highway. This leads to the increase in Cu and Commission 2015). Due to the fact that the paper industries
Pb, which could be a major source of the contamination. are far from the Yanghe River, others are the main pollu-
The industrial source of Cd could be metal plating, coating tion emission industries and accounting for nearly 95 % of
operations, transportation equipment, machinery and bak- COD pollution in the Yanghe River area. The agriculture
ing enamels, photography, television phosphors, etc. areas locate along the river, while the other industries
(Suthar et al. 2009). These manufactured products have a located near human habitats. In the upstream of the river,
close relationship with human habitat. Zn is also common domestic sewage played an inevitable role in the surface
in daily life, so Cd and Zn might come from domestic sediment contamination. With the increase in the distance
sewage. Cr is mainly controlled by the parent materials and between sampling site and Funing Town, the impact of
associated with natural processes such as weathering of domestic wastewater decreased. In the estuarine area,
rock and soil (Zhao et al. 2014). heavy metal in riverbed sediments was affected by the
Planting industry and animal industry gathered in the interaction of river runoff and tidal current. Weak tide and
Yanghe River basin. It was found that agricultural fertil- tidal current entering the Yanghe River through the mouth
izers in the river basin had close relationship with heavy will become even weaker; for example, the tidal current
metal pollution (Guo and He 2013). Farm land occupies velocity is less than 0.12 m/s at the mouth (Kuang et al.
large parts of the riverine area, and agricultural wastewater 2015), which imply that the tidal current limit (where the
can be a crucial cause of river contamination. Agrochem- maximum flood current can reach) will mainly be deter-
icals and fertilizers with heavy metal accumulate in soil mined by runoff. Since the river runoff is much stronger in
and then enter into the river system through irrigation water the flood season than that in the dry season, the tidal

123
Environ Earth Sci (2016) 75:1105 Page 11 of 13 1105

Fig. 8 Main regional


distributions in two sides of the
Yanghe River

current could reach S6 in the dry season, while it only average heavy metal concentrations in riverbed sediments
reaches S8 (very close to the mouth) in the flood season. in the Yanghe River were lower than those in the other
Therefore, the influence of saltwater intrusion leads to the reported rivers in China and in the world. No significant
sediment deposition due to flocculation of fine sediments. correlation exists between corresponding metal in water
This resulted in the enrichment of heavy metal in riverbed body and riverbed sediments, which imply that heavy metal
sediments in the estuarine area. A small tributary running in water body is not released from contaminated riverbed
through northern part of the river discharged into the sediments.
Yanghe River at S8, which brought domestic wastewater The contamination factors (CFs) showed that Cd had
into the river from Beidaihe District with dense population higher contamination level than other heavy metals in
and tourist. Hence, the estuarine area suffered more heavy riverbed sediments, and the total contamination factors of
metal contamination especially at around S8. S4 and S5, heavy metal followed the order of S8 [ S5 [ S6 [ S7 [
with high RI values in both seasons shown in Fig. 4, were S1 [ S4 [ S2 [ S3. The mean pollution load index (PLI)
situated near traffic arteries, and traffic has a close rela- in the range of 1.0–1.1 indicated a progressive deterioration
tionship with the variation of heavy metal concentrations. in riverbed sediments. The geo-accumulation index (Igeo)
revealed that the pollution decreased in the order of
Cd [ Cu [ Zn [ Pb [ Cr, with Cd having the heaviest
Conclusions polluted and Pb and Cr nearly non-pollution in riverbed
sediments.
In this work, several different tools, methods and indices The potential ecological risk index (RI) had compatible
have been employed to assess the heavy metal contami- decreasing trends with the PLI values in both flood and dry
nation in water body and riverbed sediments in the Yanghe seasons. The highest PLI and potential ecological risk index
River, China. The average concentration of heavy metal in (RI) were found in riverbed sediment samples at Site 8 near
water body was in the order of Zn [ Cu [ Pb [ Cr [ Cd, the Yanghe River mouth due to large amount of domestic
but it followed the order of Zn [ Cr [ Cu [ Pb [ Cd in wastewater from densely populated Beidaihe District and
riverbed sediments. All concentrations of heavy metal in tourists in summer. Heavy metal concentrations in riverbed
water body were much lower than the upper limit value sediments varied differently in both flood and dry seasons,
required by the drinking water quality standards, and the and the pollution in the downstream was much higher than

123
1105 Page 12 of 13 Environ Earth Sci (2016) 75:1105

that in the upstream especially in the flood season. In the Hebei Province Department of Land and Resources (2007) Marine
upstream of the river, heavy metal contamination decreased resources investigation and evaluation in Hebei Province (Vol-
ume One). China Ocean Press, Beijing
with the increasing distance from Funing Town due to Hou D, He J, Lü C et al (2013) Distribution characteristics and
decreased domestic wastewater from Funing County. potential ecological risk assessment of heavy metals (Cu, Pb, Zn,
However, in the downstream of the river, the contamination Cd) in water and sediments from Lake Dalinouer, China.
level increased while close to the river mouth because of Ecotoxicol Environ Saf 93:135–144
Hu CF (2016) Coupling simulation and analysis of hydrodynamics
dense population and tourists in the coastal zone. According and water quality in Qinhuangdao rivers, estuaries and coastal
to principal component analysis (PCA) and factor analysis waters, master dissertation of Tongji University
(FA), domestic sewage appeared to be a major source of Ip CCM, Li X, Li Y et al (2007) Trace metal distribution in sediments
heavy metal contamination in riverbed sediments, while the of the Pearl River Estuary and the surrounding coastal area,
South China. Environ Pollut 147(2):311–323
tidal current, runoff, traffic, planting industry and animal Kuang CP, He LL, Zhang Y et al (2010) Comparison of wave fields
industry also played inevitable roles. caused by four proposed beach nourishment schemes in
Beidaihe, China. J Hydrodynam B 22(5):719–725
Acknowledgments This study is financially supported by the Marine Kuang CP, Li ZY, Gu J et al (2015) Study on spatial and temporal
Public Welfare Program of China (201305003) and the Science and characteristics of the COD in estuarine and coastal waters of the
Technology Program of the Oceanic Administration of Hebei Pro- Yanghe River and the Daihe River. China Environ Sci
vince of China. 35(12):3689–3697
Li Z, Yu J, Yang M et al (2010) Cyanobacterial population and
harmful metabolites dynamics during a bloom in Yanghe
Reservoir, North China. Harmful Algae 9(5):481–488
References Liu J, Li Y, Zhang B et al (2009) Ecological risk of heavy metals in
sediments of the Luan River source water. Ecotoxicology
Barlas N, Akbulut N, Aydoğan M (2005) Assessment of heavy metal 18(6):748–758
residues in the sediment and water samples of Uluabat Lake, Liu SG, Lou S, Kuang CP et al (2011a) Water quality assessment by
Turkey. Bull Environ Contam Toxicol 74(2):286–293 pollution-index method in the coastal waters of Hebei Province
Cai JB, Li WQ, Liu N et al (2007) Characteristics of contaminated in western Bohai Sea, China. Mar Pollut Bull 62(10):2220–2229
sediments in Yanghe Reservoir. J Agro-Environ Sci Liu W, Zeng Z, Zhang R et al (2011b) Investigation report on
26(3):886–893 Qinhuangdao shellfish industry development. Mod Fish Inform
Chen JS, Liu YJ (1992) Research on heavy metals in water 26(6):10–14
environment in China. Chinese Environmental Science Publish- Loska K, Wiechula D (2003) Application of principal component
ing House, Beijing analysis for the estimation of source of heavy metal contami-
Cheng Z, Man YB, Nie XP et al (2013) Trophic relationships and nation in surface sediments from the Rybnik Reservoir.
health risk assessments of trace metals in the aquaculture pond Chemosphere 51(8):723–733
ecosystem of Pearl River Delta, China. Chemosphere Luo L, Ma Y, Zhang S et al (2009) An inventory of trace element
90(7):2142–2148 inputs to agricultural soils in China. J Environ Manage
Cook JA, Andrew SM, Johnson MS (1990) Lead, zinc, cadmium and 90(8):2524–2530
fluoride in small mammals from contaminated grass-land Morillo J, Usero J, Gracia I (2004) Heavy metal distribution in marine
established on fluorspar tailings. Water Air Soil Pollut 51:43–54 sediments from the southwest coast of Spain. Chemosphere
Cui L, Li Z (2006) Characteristics of soil phosphorus export by 55(3):431–442
surface runoff from gentle slope in Yanghe watershed. J Soil Müller G (1969) Index of geoaccumulation in sediments of the Rhine
Water Conserv 20(3):10–20 River. GeoJournal 2:108–118
Dong A, Zhai S, Zabel M et al (2012) Heavy metals in Changjiang Onodera S, Saito M, Sawano M et al (2008) Effects of intensive
estuarine and offshore sediments: responding to human activi- urbanization on the intrusion of shallow groundwater into deep
ties. Acta Oceanol Sinica 31(2):88–101 groundwater: examples from Bangkok and Jakarta. Sci Total
Fan T, Ye WL, Chen HY et al (2013) Review on contamination and Environ 404(2–3):401–410
remediation technology of heavy metal in agricultural soil. Ecol Pan Y, Kuang CP, Gu J et al (2014) Assessment of a measure for
Environ Sci 22(10):1727–1736 water exchange strengthening of artificial headland-bays based
Fu J, Zhao C, Luo Y et al (2014) Heavy metals in surface sediments on shoreline change and flushing time. J Coastal Res
of the Jialu River, China: their relations to environmental factors. 30(3):615–628
J Hazard Mater 270:102–109 Panda UC, Sundaray SK, Rath P et al (2006) Application of factor
Gaur VK, Gupta SK, Pandey SD et al (2005) Distribution of heavy and cluster analysis for characterization of river and estuarine
metals in sediment and water of river Gomti. Environ Monit water systems—a case study: Mahanadi River (India). J Hydrol
Assess 102(1–3):419–433 331(3–4):434–445
Guo R, He X (2013) Spatial variations and ecological risk assessment Pekey H (2006) The distribution and sources of heavy metals in Izmit
of heavy metals in surface sediments on the upper reaches of Bay surface sediments affected by a polluted stream. Mar Pollut
Hun River, Northeast China. Environ Earth Sci 70(3):1083–1090 Bull 52(10):1197–1208
Hakanson L (1980) An ecological risk index for aquatic pollution Phiri O, Mumba P, Moyo BHZ, Kadewa W (2005) Assessment of the
control: a sedimentological approach. Water Res 14(8):975–1001 impact of industrial effluents on water quality of receiving rivers
Hebei Development and Reform Commission (2015) The land in urban areas of Malawi. Int J Environ Sci Technol
pollution source investigation and industrial structure optimiza- 2(3):237–244
tion in Beidaihe area. Hebei Development and Reform Com- Qi S, Leipe T, Rueckert P et al (2010) Geochemical sources,
mission, Hebei deposition and enrichment of heavy metals in short sediment

123
Environ Earth Sci (2016) 75:1105 Page 13 of 13 1105

cores from the Pearl River Estuary, Southern China. J Mar Syst The Yangtze Water Environment Monitoring Center (2013) Regula-
82:S28–S42 tion for water environmental monitoring. SL219–98
Segura R, Arancibia V, Zúñiga MC et al (2006) Distribution of Varol M (2011) Assessment of heavy metal contamination in
copper, zinc, lead and cadmium concentrations in stream sediments of the Tigris River (Turkey) using pollution indices
sediments from the Mapocho River in Santiago, Chile. and multivariate statistical techniques. J Hazard Mater
J Geochem Explor 91(1–3):71–80 195:355–364
Shao DG, Song XY, Xia J et al (1999) Research on real-time optimal Varol M, Şen B (2009) Assessment of surface water quality using
flood dispatching model for Yanghe Reservoir. Adv Water Sci multivariate statistical techniques: a case study of Behrimaz
10(02):36–40 Stream, Turkey. Environ Monit Assess 159(1–4):543–553
Simeonov V, Massart DL, Andreev G et al (2000) Assessment of Varol M, Şen B (2012) Assessment of nutrient and heavy metal
metal pollution based on multivariate statistical modeling of ‘hot contamination in surface water and sediments of the upper Tigris
spot’ sediments from the Black Sea. Chemosphere 41(9): River, Turkey. Catena. 92:1–10
1411–1417 Wang LP, Zheng BH (2013) Eutrophication development and its key
Sin SN, Chua H, Lo W et al (2001) Assessment of heavy metal affected factors in the Yanghe Reservoir. Acta Ecologica Dinica
cations in sediments of Shing Mun River, Hong Kong. Environ 33(3):1011–1017
Int 26(5–6):297–301 Ward J (1963) Hierarchical grouping to optimize an objective
Singh KP, Malik A, Mohan D et al (2004) Multivariate statistical function. J Am Stat Assoc 301(58):236–244
techniques for the evaluation of spatial and temporal variations Yuan X, Zhang L, Li J et al (2014) Sediment properties and heavy
in water quality of Gomti River (India)—a case study. Water Res metal pollution assessment in the river, estuary and lake
38(18):3980–3992 environments of a fluvial plain, China. Catena 119:52–60
State Environment Protection Agency (2004) The technical specifi- Zhang LY, Wang SR, Chu ZS et al (2010) Distribution characteristics
cation for soil environment monitoring. HJ/T 166-2004 of phosphorus in sediment of Yanghe Reservoir and in soil of its
Suresh G, Ramasamy V, Meenakshisundaram V et al (2011) Influence basin. China Environ Sci 30(11):1529–1536
of mineralogical and heavy metal composition on natural Zhao Y, Xia XH, Yang ZF et al (2012) Assessment of water quality in
radionuclide concentrations in the river sediments. Appl Radiat Baiyangdian Lake using multivariate statistical techniques.
Isot 69(10):1466–1474 Procedia Environ Sci 13:1213–1226
Suthar S, Nema AK, Chabukdhara M et al (2009) Assessment of Zhao L, Xu Y, Hou H et al (2014) Source identification and health
metals in water and sediments of Hindon River, India: impact of risk assessment of metals in urban soils around the Tanggu
industrial and urban discharges. J Hazard Mater 171(13): chemical industrial district, Tianjin, China. Sci Total Environ
1088–1095 468–469:654–662

123

You might also like