Marine Pollution Bulletin xxx (2015) xxxxxx

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Marine Pollution Bulletin

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Baseline

Spatial and seasonal characteristics of dissolved heavy metals in the east

and west Guangdong coastal waters, South China
Ling Zhang a, Zhen Shi b, JingPing Zhang a, Zhijian Jiang a, Fei Wang c, Xiaoping Huang a,
a
CAS Key Laboratory of Tropical Marine Bio-resources and Ecology, South China Sea Institute of Oceanology, Chinese Academy of Sciences, Guangzhou 510301, China
b
State Key Laboratory of Tropical Oceanography, South China Sea Institute of Oceanology, Chinese Academy of Sciences, Guangzhou 510301, China
c
State Key laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China

a r t i c l e i n f o a b s t r a c t

Article history: Heavy metal concentrations and physicochemical parameters in seawater were measured in Guangdong
Available online xxxx coastal waters, South China. Results showed that the concentrations and distribution of heavy metals var-
ied spatially and seasonally. Generally, heavy metal concentrations in the east regions were higher than
Keywords: in the west. Concentrations of Pb, Zn, Cd and Cr in wet seasons were generally higher than in dry seasons
Dissolved heavy metal owing to the seasonal differences of the river discharge, rainfall and seawater intrusion. Principal compo-
Spatial and seasonal variation nent (PC) analysis showed that PC1, PC2 and PC3 in the east were correlated to Pb + Cr + Zn + Cd, As + Cd
Sources
and Cu, respectively, and they were correlated to Pb + Cr, Zn + Cu + Cd and As + Cu, respectively, in the
South China
west. That was maybe due to the differences of local heavy metal sources. The anthropogenic activities
contributed more to the main sources of heavy metals, and contamination factors indicated that Zn
and Pb pollution was serious in study area.
2015 Elsevier Ltd. All rights reserved.

Escalating human populations and economic development have
signicantly contributed to the current worldwide deterioration in
water quality, including accumulation of heavy metals in the aqua-
tic environment (Pertsemli and Voutsa, 2007; Krishna et al., 2009;
Li and Zhang, 2010; Varol, 2013). Heavy metals are non-biodegrad-
able, tending to rapidly accumulate in the environment and are
able to reach toxic levels in short period, but, their removal is
rather difcult and sometimes impossible. Nowadays, heavy met-
als originating from human activities are frequently detected in
sediments and water column (Sun et al., 2010; Huang et al.,
2012). In the aquatic environments, heavy metals are derived from
a variety of natural and anthropogenic sources, such as atmo-
spheric deposition, geologic weathering, agricultural activities,
residential and industrial products (Soriano et al., 2012; Wang
et al., 2012a; Li et al., 2013). Anthropogenic activities, particularly
electroplating, mining and mineral processing etc. have been
greatly inuencing the local and global geochemical cycles of
heavy metals (Jiann and Wen, 2009; Dou et al., 2013), which has
attracted more and more public concerns in recent decades
(Beltrame et al., 2009; Varol, 2011; Gao and Li, 2012).
Corresponding author.
E-mail address: xphuang@scsio.ac.cn (X. Huang).
With rapid urbanization and industrialization, coastal areas in
China are now facing great challenges in regard to heavy metal
contamination (Ip et al., 2007; Sun et al., 2009; Wang et al.,
2012a). Guangdong Province (GD) is adjacent to the South China
Sea with the longest coastline of 3.37  106 m in China, which dis-
plays from north-east to south-west and there are more than ten
important industrial cities along the coastline. As one of the most
developed industrial areas in China and the manufacturing base
in the world, GD coastal regions have been exposed for several dec-
ades to a high human pressure as a result of high population and
industrial densities and intensive agricultural activities. Large
amounts of pollutants (nutrients, toxic metals and persistent
organic pollutants) have been discharged into the coastal waters
(Zhang et al., 2009; Yin et al., 2011; Wang et al., 2012a,b; Qiao
et al., 2013). In combination with the long residence time of these
pollutants, they present a preoccupying threat to the coastal
ecosystem. Among the various contaminants, heavy metals are of
particular concern due to their environmental persistence, biogeo-
chemical recycling and ecological risks. The Pearl River Estuary
(PRE) was the largest estuary in GD with abundant studies (Ip
et al., 2007; Chen et al., 2012; Zhang et al., 2013). There were also
some other researches in coastal waters in GD (Zhang et al., 2011;
Wang et al., 2013; Xu et al., 2014). However, previous studies
mainly focused on the sediments, or the work was carried out in
limited waters. That was to say, the research work about dissolved

http://dx.doi.org/10.1016/j.marpolbul.2015.03.035
0025-326X/ 2015 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Zhang, L., et al. Spatial and seasonal characteristics of dissolved heavy metals in the east and west Guangdong coastal
waters, South China. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.03.035
2 L. Zhang et al. / Marine Pollution Bulletin xxx (2015) xxxxxx

Fig. 1. Map showing the Guangdong coastal regions and the study areas with sampling sites.

heavy metals were still very scare in the east and west GD coastal
regions, which are signicant as the important supporting-area to
the Pearl River Delta. More importantly, with the call for sustain-
able development and marine environmental conservation, it is
of great signicance in the present day to speed up the comprehen-
sive understanding of the whole coastal regions in GD. Therefore,
an integrated research about the heavy metals in this area would
be a reference and the base for further study. For this purpose, in
this work, 29 sites were selected and 108 surface seawater samples
were collected in four seasons during 20062007 in GD coastal
waters (divided into the east and west regions excluding the
PRE). At the same time, dissolved heavy metal concentrations
(Cu, Pb, Zn, Cr, Cd and As) and the physicochemical parameters
in seawater were measured. The objectives of this study are (1)
to investigate the spatial and seasonal variations of dissolved
heavy metal distribution in the east and west GD coastal waters;
(2) to discuss the possible sources of heavy metals and to assess
the metal contamination in seawater. To our knowledge, there
was no integrated research like our study about the dissolved
heavy metals in GD coastal waters. This research will help to estab-
lish the scientic data set for the study of the ecological and
environmental quality in this signicant subtropical coastal area.
In this work, the study area is mainly divided into four parts
from the east to the west along the GD coastline, including
Shantou area, Shanhui area (the East GD coastal waters),
Yangmao area and Zhanjiang area (the West GD coastal waters,
Fig. 1). The seawater samples in the east were mainly collected
in Zhelin Bay, Shantou Harbor, Shanwei Harbor, Daya Bay,
Dapeng Bay and their adjacent waters. The samples in the west
were collected from Hailing Bay, Shuidong Harbor, Zhanjiang
Harbor, Leizhou Harbor, Liusha Bay and their adjacent waters.
Sampling was carried out in spring (April), summer (July), autumn
(November) and winter (December). Water samples were collected
using a 5-L Niskin bottles from 0.5 m below the surface at each site.
100 ml seawater for total organic carbon (TOC) analysis was trans-
ferred to a glass bottle previously washed with HNO3. The water
samples for metal and nutrient determination were ltered imme-
diately through 0.45 lm pore glass ber lter (GF/F, Whatman),

Please cite this article in press as: Zhang, L., et al. Spatial and seasonal characteristics of dissolved heavy metals in the east and west Guangdong coastal
waters, South China. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.03.035
 L. Zhang et al. / Marine Pollution Bulletin xxx (2015) xxxxxx 3

12 9
Spring Summer Autumn Winter Spring Summer Autumn Winter
a 8.8
10 8.6
b
8.4
8

DO (mg/L)
8.2

pH
6 8
7.8
4 7.6
7.4
2
7.2
0 7
Shantou Shanhui Yangmao Zhanjiang Shantou Shanhui Yangmao Zhanjiang

120 6
Spring Summer Autumn Winter Spring Summer Autumn Winter
100 c 5 d

TOC (mg/L)
80 4
SPM

60 3

40 2

20 1

0 0
Shantou Shanhui Yangmao Zhanjiang Shantou Shanhui Yangmao Zhanjiang

45 1.2
Spring Summer Autumn Winter Spring Summer Autumn Winter
40 e
35
DN+DP (mg/L) 1 f
30 0.8
Salinit

25
0.6
20
15 0.4
10
0.2
5
0 0
Shantou Shanhui Yangmao Zhanjiang Shantou Shanhui Yangmao Zhanjiang

Fig. 2. The seasonal and regional variations of physicochemical parameters in seawater. Shantou, Shanhui, Yangmao and Zhanjiang are the four areas from the east to the
west in Guangdong coastal regions.

and then the samples for metal analysis were acidied to pH 1.5
2.0 with HNO3. Suspended particulate material (SPM) samples
were ltered through pre-weighed Whatman GF/F ber lters
(25 mm). The lters and the water samples were stored in a
20 C refrigerator. The seawater for DO analysis was collected
with a tube reaching the bottom of bottle until the water
overowed.
The surface seawater salinity was measured in situ with a multi-
parameter sensor YSI6600, and pH values were determined with a
pH meter. DO was determined using the Winkler titration method
according to Gao and Song (2008) just after sampling. The SPM
samples were dried and weighed to determine the amount in mg/
L of samples. DOC concentrations were measured with a liquiTOC
II analyzer. Dissolved nitrogen (DN) and phosphorus (DP) were
measured using the approach according to Valderrama (1981).
The pretreatment and analysis of metals in seawater samples were
carried out according to the method of Ju (2004) with a minor modi-
cation. Concentrations of Cu, Pb, Zn, Cr and Cd were determined
using atomic absorption spectrometry, and As concentrations were
determined using the atomic uorescence spectrometer. The rela-
tive standard deviations for precision were 5.2%, 3.9%, 6.9%, 3.2%,
4.2% and 2.36% for Cu, Pb, Zn, Cr, Cd and As, respectively.
The contamination factor (CF) is the ratio obtained by dividing
the concentration of each heavy metal in the water (Cs) by the
background concentration (Cb) (Eq. (1)):
CF C s =C b
CF values are interpreted as follows: low contamination, CF < 1;
moderate contamination, 1 < CF < 3; considerable contamination,
3 < CF < 6; and very high contamination, CF > 6 (Hakanson, 1980).
Correlations between heavy metals may reect some informa-
tion of origin and migration about these elements. For example,
high correlation between two heavy metals probably means these
two elements share similar pollution sources or they share analo-
gous transformation and migration processes in the certain cir-
cumstances. Therefore, Pearson correlation analysis and principal
component analysis (PCA) were applied to the data to explore
the correlations between the heavy metals, as well as between
the metals and the concerned physicochemical parameters in
seawater.
The physicochemical parameters of seawater were illustrated in
Fig. 2. In general, DO concentrations slightly varied with the areas
and seasons (Fig. 2a). Relatively high DO was found in spring
(8.73 0.92 mg/L in Shantou area) and winter (7.92 0.27 and
7.54 0.39 mg/L in Yangmao and Zhanjiang areas, respectively).
pH was 8.15 0.20 with the lowest value occurred in Shantou area
in summer (7.71 0.32, Fig. 2b). DO and pH values in coastal
waters were inuenced by runoff, precipitation, temperature etc
(Zhang et al., 2014). Furthermore, they were also affected by organ-
ism activities. For instance, strong photosynthesis will elevate the
DO levels in water during the growth of phytoplankton, but the
decomposition of red tide plankton would dramatically decrease
the DO in water (Shi et al., 2005). SPM concentrations were high
in Shantou area (28.19 29.76 mg/L) with the highest value found
in autumn (Fig. 2c). DOC concentrations obviously varied between
seasons with the highest and lowest values of 2.15 0.41 and
1
2.86 0.2 mg/L, in autumn and winter, respectively, (Fig. 2d).
Salinity of seawater generally changed slightly except that there
was a lower value of 10.25 11.23 in Shantou area in summer
(Fig. 2e), which may be related to the strong runoff from local

Please cite this article in press as: Zhang, L., et al. Spatial and seasonal characteristics of dissolved heavy metals in the east and west Guangdong coastal
waters, South China. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.03.035
4 L. Zhang et al. / Marine Pollution Bulletin xxx (2015) xxxxxx

Table 1
Dissolved heavy metal concentrations (Con., lg/L) in surface seawater.

Region Season Con. Cu Pb Zn Cr Cd As

East GD coastal regions
ShanTou area Spring Range 1.42.9 0.41.6 6.09.0 0.40.7 0.020.11 2.05.1
Mean 2.3 1.1 6.8 0.5 0.07 3.1
Summer Range 1.42.9 0.25.9 1.682.7 nd 0.230.42 1.21.2
Mean 2.0 3.2 28.9 nd 0.29 1.2
Autumn Range 1.62.6 0.31.4 7.016.0 0.63.4 0.030.05 0.91.8
Mean 2.1 0.9 10.6 1.8 0.04 1.4
Winter Range 1.75.0 01.8 6.019.0 nd 0.030.16 2.05.5
Mean 2.6 0.6 12.0 nd 0.08 4.0
ShanHui area Spring Range 1.43.6 0.82.8 4.020.0 0.41.0 0.050.17 0.66.0
Mean 2.3 1.9 10.8 0.6 0.08 3.4
Summer Range 0.29.3 0.47.7 1.648.3 nd8.2 0.050.66 02.0
Mean 2.4 4.9 22.0 8.2 0.23 1.3
Autumn Range 1.63.1 0.43.3 5.020.0 0.67.5 0.010.04 0.72.0
Mean 2.5 1.5 10.5 2.5 0.03 1.4
Winter Range 0.83.3 nd2.9 7.019.0 nd 0.030.06 1.66.4
Mean 1.7 1.4 10.8 nd 0.05 4.0
West GD coastal regions
YangMao area Spring Range nd3.2 0.11.3 2.244.0 00.7 0.050.26 03.5
Mean 2.2 0.5 12.9 0.5 0.12 2.1
Summer Range 1.32.6 0.44.0 1.629.9 nd 0.020.40 1.23.1
Mean 1.9 2.3 12.7 nd 0.10 1.7
Autumn Range 1.33.6 1.16.5 5.010.0 0.74.0 0.040.19 0.51.3
Mean 2.3 4.2 8.0 2.3 0.10 0.9
Winter Range 1.72.5 0.44.5 4.016.0 0.31.6 0.050.12 1.66.0
Mean 2.1 1.5 9.5 0.9 0.09 4.1
Zhanjiang area Spring Range nd2.9 nd2.1 2.027.0 0.92.6 0.040.10 nd2.6
Mean 2.02 1.2 18.8 1.5 0.07 1.67
Summer Range 0.318.1 0.43.3 7.181.8 0.91.9 0.010.89 1.211.8
Mean 1.3 2.4 14.2 1.6 0.05 1.7
Autumn Range 0.92.8 0.21.4 6.026.0 0.11.5 0.040.12 0.93.0
Mean 1.8 0.7 12.3 0.8 0.08 1.4
Winter Range 0.72 0.46.2 2.09.0 nd1.7 0.060.17 nd2.2
Mean 1.7 1.7 6.5 1.4 0.12 1.3

nd is no data.

rivers (i.e. Han River and Rong River) in wet seasons. DN + DP con-
centrations showed obvious variations according to seasons and
areas, with the highest value in Shantou area (Fig. 2f). The high
concentrations of SPM, DN + DP in Shantou area mainly came from
the runoff and sewage discharge. Especially, prosperous aquacul-
ture in Shantou area resulted in abundant nutrient inputs to the
coastal waters.
Dissolved heavy metal concentrations were listed in Table 1.
Concentrations of Cu, Pb, Zn, Cr, Cd and As in the east waters were
2.24 1.20, 1.94 1.87, 14.05 12.17, 1.20 1.88, 0.11 0.12 and
2.48 1.59 lg/L, respectively, which ranked following the order
of Zn > As > Cu > Pb > Cr > Cd. The concentrations of Cu, Pb, Zn, Cr,
Cd and As in the west waters were 1.91 2.30, 1.81 3.19,
11.86 12.74, 1.27 0.83, 0.09 0.12 and 1.86 1.57 lg/L, and
they ranked as Zn > Cu > As > Pb > Cr > Cd. Generally, the concen-
trations of Cu, Pb, Zn, Cd and As in the east waters were higher than
in the west, which was tightly related to the local economy and
urbanization development in the two regions. Previous study in
the east coastal waters showed that concentrations of Cu, Pb, Zn,
Cr, Cd and As were 3.2, 2.4, 42.2, 2.34, 0.041 and 2.25 lg/L (in
Daya Bay, Qiu et al., 2005), respectively, and concentrations of
Cu, Pb, Zn, Cr and Cd were 4.16, 0.34, 9.03, 6.00 and 0.075 lg/L
(in Dapeng Bay, Huang et al., 2005), respectively. Above metal con-
centrations were generally within the ranges in our study, except
that concentrations of Cd and As in Daya Bay and of Pb in
Dapeng Bay. Reported concentrations of Cu, Pb, Cd and As in
Shuidong Harbor were 5.29, 2.51, 0.01 and 0.42 lg/L (Niu et al.,
2007), respectively. Thereinto, Pb and As concentrations were com-
parable with those in our study, while the concentrations of Cu and
Cd were beyond the ranges in Yangmao area in our study.
The concentrations of Cu, Pb, Zn, Cr, Cd and As in the whole
study area were 2.08 1.83, 1.88 2.61, 12.96 12.38,
1.24 1.50, 0.10 0.12 and 2.17 1.70 lg/L, respectively.
Referring to other studies in several famous coastal regions in
China, the concentrations of Cu, Pb, Zn, Cr and Cd in Changjiang
estuarine and coastal waters were 0.96, 0.68, 7.56, 0.39 and
0.08 lg/L, respectively (Sun et al., 2009), and the concentrations
of Cu, Pb, Zn, Cd and As in Beibu Bay coastal waters were 0.7,
2.1, 19.9, 0.05 and 0.76 lg/L (Jiang et al., 2013). Our metal concen-
trations were higher than the values in Changjiang estuarine and
Beibu Bay coastal waters, except that Pb and Zn concentrations
in our study were lower than those in Beibu Bay coastal waters,
indicating that heavy metal concentrations in GD coastal waters
were relatively high.
Cu concentrations in Shantou, Shanhui and Yangmao areas were
relatively high (Fig. 3a). Shanhui area had the highest Pb concen-
tration (2.43 1.08 lg/L) and followed by Yangmao area
(2.13 1.17 lg/L) (Fig. 3b). The highest Zn concentration was
found in Shantou area (14.58 11.05 lg/L), then in Shanhui and
Zhanjiang areas (Fig. 3c). Cr concentrations were high in Shanhui
(1.38 0.67 lg/L) and Zhanjiang (1.35 0.52 lg/L) areas (Fig. 3d).
Shantou area had the highest Cd concentration (0.12 0.05 lg/L),
then followed by Yangmao area (Fig. 3e). Concentrations of As
were relatively high except in Zhanjiang area (Fig. 3f).
Throughout above results, concentrations of Cu, Zn and Cd were
the highest in Shantou area, at the same time, concentrations of
Pb, Cr and As were the highest in Shanhui area. Although the low-
est concentrations of Cu, Cd and As occurred in Zhanjiang area,
concentrations of Zn and Cr in this area were found to be high,
implying that the heavy metal contamination in Zhanjiang area

Please cite this article in press as: Zhang, L., et al. Spatial and seasonal characteristics of dissolved heavy metals in the east and west Guangdong coastal
waters, South China. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.03.035
 L. Zhang et al. / Marine Pollution Bulletin xxx (2015) xxxxxx 5

8 10
Spring Summer Autumn Winter Spring Summer Autumn Winter
9
7 a 8
b
6
7
5

Cu (ug/L)
6

Pb (ug/L)
4 5
4
3
3
2
2
1 1
0 0
Shantou Shanhui Yangmao Zhanjiang Shantou Shanhui Yangmao Zhanjiang

70 10
Spring Summer Autumn Winter Spring Summer Autumn Winter
9 d
60 c
8
50 7
Zn (ug/L)

Cr (ug/L)
40
5
30
4
20 3
2
10
1
0 0
Shantou Shanhui Yangmao Zhanjiang Shantou Shanhui Yangmao Zhanjiang

0.5 7
Spring Summer Autumn Winter Spring Summer Autumn Winter
e 6 f
0.4
5
Cd (ug/L)

As (ug/L)

0.3 4

3
0.2
2
0.1
1

0 0
Shantou Shanhui Yangmao Zhanjiang Shantou Shanhui Yangmao Zhanjiang

Fig. 3. The seasonal and regional variations of dissolved heavy metal concentrations in seawater. Shantou, Shanhui, Yangmao and Zhanjiang are the four areas from the east
to the west in GD coastal regions.

shouldnt be ignored. All the heavy metal concentrations in this
study exhibited seasonal variations (Fig. 3). Concentrations of Pb
and Cr in wet seasons were obviously higher than in dry seasons
in Shantou, Shanhui and Yangmao areas, as well as concentrations
of Zn and Cd in Shantou and Shanhui areas, which may be attribu-
ted to the seasonal differences of the river discharge and the rain-
fall. Because Pb, Zn, Cr and Cd in this area were mainly derived
from the runoff and the industrial and agricultural efuent dis-
charge, and the atmospheric deposition was another important
source for heavy metals (Ip et al., 2007; Wang et al., 2012b;
Wang et al., 2013). The salinity and nutrients were the important
factors affecting the concentration of Cr (Sun et al., 2009), and good
negative correlation was shown between salinity and concentra-
tion of Cr (Table 2, R = 0.409, p < 0.05), suggesting that the low
salinity would hamper the mixing of water and maintain the high
level of Cr in surface water. In contrast, the highest As concentra-
tions were found in winter except in Zhanjiang areas, and the good
positive correlation between As and salinity (Table 2, R = 0.294,
p < 0.05) in the east coastal waters indicated that concentration
of As was mainly inuenced by the intrusion of seawater in dry
seasons. Moreover, the reduction of runoff in dry seasons
decreased the dilution effect on the metal concentration.
The results of Pearson correlation analysis were shown in
Table 2. The signicant positive correlations between PbZn, Cd,
Cr (R = 0.576, 0.424, 0.578, respectively, P < 0.01), and ZnCd,
Cr (R = 0.538, 0.581, respectively, p < 0.01), as well as CdAs
(R = 0.270, p < 0.05) suggested that these heavy metals maybe
shared the similar sources in the east coastal regions. It was nota-
ble that the weak correlations between metals in the west regions
were obtained except Pb and Cr (R = 0.640, p < 0.01), which maybe
was attributed to the more complex metal sources in west regions.
The results of PCA for metal concentrations were shown in Table 3
and plotted in Fig. 4. Three factors with eigenvalues higher than 1
in the east and west regions were extracted, respectively. The fac-
tors were dominated by different metal combination in the two
regions. PC1, PC2 and PC3 in the east were correlated to
Pb + Cr + Zn + Cd, As + Cd and Cu, respectively, and they were cor-
related to Pb + Cr, Zn + Cu + Cd and As + Cu, respectively, in the
west. That maybe was explained by the different sources of metals
and the inuencing factors in the two regions. There were gener-
ally no signicant correlations between metals and physicochemi-
cal parameters in seawater in this study except DO-Cr, -Zn and
salinity-As, -Cd, and pH-Pb. The correlations between heavy metals
and the physicochemical parameters depended on the chemical
properties and migration forms of the elements, and were also
restrained by the variations of the parameters in situ (Ke, 1991).
In present study, the external inputs (terrestrial, anthropogenic,
sedimentary) of heavy metals appeared to play a more important
role than the hydrography and biogenic processes (Gavriil and
Angelidis, 2005). The high heavy metal concentrations in GD
coastal regions were mainly attributed to the anthropogenic activi-
ties through sewage discharge and atmospheric deposition (Qiao
et al., 2013; Wang et al., 2013; Zhang et al., 2013). However, the
detailed heavy metal sources were different between the east

Please cite this article in press as: Zhang, L., et al. Spatial and seasonal characteristics of dissolved heavy metals in the east and west Guangdong coastal
waters, South China. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.03.035
6 L. Zhang et al. / Marine Pollution Bulletin xxx (2015) xxxxxx

Table 2
Pearson correlations matrix for dissolved heavy metal concentrations and the physicochemical parameters in seawater.

DO pH Salinity SPM DOC DN DP Cu Pb Zn Cd As Cr

DO (58) 1
pH (58) .244 1 East GD coastal waters
Salinity (58) .053 586** 1
SPM (58) .024 .196 .205 1
DOC (58) .304* .045 .123 .057 1
DN (58) .017 .569** .761** 354** .075 1
DP (58) .096 .144 .108 .337** .074 .564** 1
Cu (58) .033 .023 .030 .026 .017 .114 .141 1
Pb (58) .035 .314* .078 .294* .065 .323* .241 .208 1
Zn (58) .124 .125 .050 .113 .144 .041 .117 .114 .576** 1
Cd (58) .090 .021 .424 .079 .080 .214 .098 .078 .424** 538** 1
As (58) .052 .024 .294* .184 .033 .039 .018 .189 .341** .255 .270* 1
Cr (30) .517** .350 .087 .090 .005 .001 .219 .113 .578** 581** .037 .295 1
DO (50) 1
pH (50) .235 1 West GD coastal waters
Salinity (50) .142 .255 1
SPM (50) .004 .225 .123 1
DOC (50) .028 .248 .208 .138 1
DN (50) .252 .004 .397* .235 .047 1
DP (50) .023 .388** .076 .327* .004 .069 1
Cu (50) .129 .225 .098 .088 .057 .190 .026 1
Pb (50) .077 .279* .162 .010 .171 .473** .380** .098 1
Zn (50) .340* .045 .229 .276 .008 .039 .060 .118 .111 1
Cd (50) .049 .142 .067 .025 .087 .033 .015 .072 .278* .062 1
As (50) .149 .050 .235 .082 .001 .135 .054 .140 .203 .008 .123 1
Cr (26) .083 .232 .409* .026 .012 .369 .189 .309 .640** .113 .155 .369 1

Numbers in the parentheses were the sample numbers.

Bold values are signicant.
*
Correlation is signicant at the 0.05 level (two-tailed).
**
Correlation is signicant at the 0.01 level (two-tailed).

Table 3 engineering, toy making, clothing industry, medical industry and

PCA results of the dissolved heavy metal concentrations.
electronic industry. The industrial pollutant discharges entered
PC1 PC2 PC3 the waters from coastal cities (Shantou, Shanhui, etc.) or some
East Zn (0.882) As (0.849) Cu (0.722) other cities through Han River, Rong River and other rivers
Pb (0.788) Cd (0.521) (Fig. 1). Especially, Han River is the second largest river in terms
Cr (0.742) of discharge in GD, which runs through Chaoshan plain and some
Cd (0.604)
important industrial cities including Chaozhou, Jieyang, so it brings
Eigenvalue 2.45 1.40 1.06
% of variance 40.82 23.34 17.62 a large amount of pollutants to the coastal zones. In contrast, the
Cumulative variance 40.82 64.16 81.78 west coastal regions were famous for heavy industries, such as
West Pb (0.862) Zn (0.753) Cu (0.679) electric power industry, mining industry, petroleum industry and
Cr (0.784) Cu (0.626) As (0.671) shipbuilding industry. On the other hand, the atmosphere input
Cd (0.541) was an important source for heavy metals in this area (Zhou
Eigenvalue 2.22 1.45 1.22
et al., 2007; Wang et al., 2013), which was attributed to the waste
% of variance 37.05 24.18 20.31
Cumulative variance 37.05 61.23 81.54
gas and dust resulted from industries, fuel-burning etc. In general,
heavy metal contamination in the west coastal regions was less
serious than in the east. However, the metal concentrations in
the west regions still remained high levels, especially Cu, Pb, Zn
and west regions due to the disparity of industrial structure, which
and Cr. Heavy metals in Yangmao areas were mainly derived from
discharged sewage containing various heavy metals. The east
the industrial and agricultural waste discharges produced by
regions were famous for light industries, such as chemical

East West

Fig. 4. The PCA plot of dissolved heavy metal concentrations.

Please cite this article in press as: Zhang, L., et al. Spatial and seasonal characteristics of dissolved heavy metals in the east and west Guangdong coastal
waters, South China. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.03.035
 L. Zhang et al. / Marine Pollution Bulletin xxx (2015) xxxxxx 7

Table 4
Dissolved heavy metal concentrations in seawater in comparison with those in some other regions in the world (lg/L).

Region Cu Pb Zn Cr Cd As Source
East GD coastal waters 2.24 1.94 14.05 1.20 0.11 2.48 This study
West GD coastal waters 1.91 1.81 11.86 1.27 0.09 1.86 This study
Jinzhou Bay, China 3.06 0.61 11.87 nd 0.92 2.19 Wang et al. (2012a)
Belgian coastal zone 3 0.14 12 nd 0.21 nd Gao et al. (2013)
Coast of Saronikos Gulf, Greece 2.80 2.85 4.21 nd 0.32 nd Ladakis et al. (2007)
The Pearl River Estuary, China 1.64 1.61 13.54 nd 0.12 2.55 Zhang et al. (2013)
Changjiang Estuary, China 0.96 0.68 7.56 0.39 0.06 nd Sun et al. (2009)
Port Jackson Estuary, Australia 0.932.55 nd nd9.66 nd 0.010.10 nd Hatje et al. (2003)
Seine Rivers, Paris 2.23 0.35 nd nd 0.03 0.75 Elbaz-Poulichet et al. (2006)
The Krka River, Croatia 1.72 0.08 0.93 nd 0.011 nd Cukrov et al. (2008)
The South China Sea 0.242.6 0.0310.2 1.0139 0.310.86 0.040.91 0.202.3 Li et al. (2013)
The Pacic water 0.08 0.01 0.05 0.2 0.001 nd Zhou et al. (2007)
The background valuea 0.010.04 0.0050.015 0.01 nd 0.01 nd Wu and Zeng (1983)
The background valueb 0.084 0.057 0.076 nd 0.006 nd Yu (2003)

nd is no data.
a
The background value of natural surface sea water.
b
The background value in the South China Sea.

Table 5
Yangjiang, Maoming and other cities through Moyang River and
The dissolved heavy metal contamination factors (CF) in seawater.
Jian River. Zhanjiang is an important industrial city and
Zhanjiang Harbor is a large-scale dock for the crude oil, container Area CF Cu Pb Zn Cr Cd
and so on. In the circumstances, Zhanjiang coastal region has Shantou Range 2431 1055 79336 39 748
become the acceptor of the pollutants from around areas, which Mean 27 25 169 5 20
Shanhui Range 2030 2586 122256 313 538
contributed more to the high levels of heavy metals in seawater,
Mean 26 43 157 7 16
especially Zn and Cr (Huang et al., 2012). Yangmao Range 2327 974 93150 312 1520
In order to put the study area into context within the global Mean 25 37 125 6 17
marine and estuarine systems, heavy metal data in current study Zhanjiang Range 1522 1242 76218 48 820
were compared with those in other regions in the world. As can Mean 20 26 151 7 13
Whole area Mean 25 33 151 6 17
be seen from Table 4, concentrations of Cu, Pb, Zn and Cd were
at the ranges of the metal concentrations in the South China Sea Background values of Cu, Pb, Zn and Cd were from the South China Sea. Background
(Li et al., 2013). In contrast, Cr in the whole study area and As in values of Cr was from the Pacic water.
Bold values mean serious contamination.
the east exceeded the highest concentrations in the South China
Sea. Generally, the concentrations of Cu, Zn and Cd in our study
were in the middle levels of the listed concentrations, but the con-
contamination factors (CF) were presented in Table 5. The results
centrations of Cr, Pb and As were higher than the listed data. These
showed that the concentrations of Cu, Pb, Cr and Cd in study area
differences may be not only related to the substances, sediment,
were 25, 33, 6 and 17 times higher than the background values,
and the emission of pollutants caused by industrial and mining
respectively. Concentration of Zn was 151 times higher than the
enterprises in estuarine delta, but also be affected by physical
corresponding background concentration. In general, the heavy
chemical properties in the environments, such as seawater salinity,
metal contamination in GD coastal waters seemed to be noticeable,
temperature, tidal currents and other effects (Lin et al., 2013). It
and more management and treatment should be introduced in
was notable that concentrations of Cu and Pb in this study were
order to protect the marine environment.
higher than those in the PRE (Zhang et al., 2013). The PRE was gen-
erally known severely impacted by anthropogenic activities these
years (Bttcher et al., 2010; Ye et al., 2012; Chen et al., 2012). Acknowledgements
The lower metal concentrations in the PRE relative to those in
our study may be partly attributed to the dilution effect by large This work was supported by the National Basic Research
freshwater inputs in the estuary. On the other hand, along with Program of China (973 Program, 2015CB452905), the Strategic
large freshwater inputs and sediment loadings, a series of geo- Priority Research Program of the Chinese Academy of Sciences
chemical and physical reactions, such as particle adsorption and (No. XDA11020205) and the National 908 Special Project of
transfer into the sediment, removed part dissolved metals from China (No. GD908-JC-06). We appreciate Dr. Wang Z.Y. (SCSIO)
the water in the PRE (Wang et al., 2012b). and Dr. Yang Y.Q. (GIG) for some valuable advice. We also sincerely
The natural background concentration of an element is com- thank Engineer Zhang G.X. (SCSIO) for the analysis of heavy metal.
monly dened as the natural quantity of a given element in a cer- Comments by anonymous reviewers improved this paper signi-
tain material (in absence of external pollution), which is cantly, and we also appreciate the arduous work of the editors.
fundamental for the evaluation of soil and water pollution. In the
present study, the background concentrations of metals in the References
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