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Kuang (2016) Article - AssessmentOfHeavyMetalContamin
Kuang (2016) Article - AssessmentOfHeavyMetalContamin
DOI 10.1007/s12665-016-5902-0
THEMATIC ISSUE
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
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Environ Earth Sci (2016) 75:1105 Page 3 of 13 1105
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
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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)
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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 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
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
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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
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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.
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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
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.
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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
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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
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