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ORIGINAL ARTICLE
Geochemical characteristics of heavy metals in coastal sedimentsfrom the northern Beibu Gulf (SW China): the background levelsand recent contamination
Peng Xia • Xianwei Meng • Aiping Feng •
Ping Yin • Jun Zhang • Xiangqin Wang
Received: 22 June 2010 / Accepted: 31 August 2011 / Published online: 29 September 2011
� Springer-Verlag 2011
Abstract Four sediment cores and one hundred surface
sediments were collected from the intertidal zone of the
northern Beibu Gulf (SW China). In order to detect the
intensity of metal contamination recently, the background
levels were successfully established for Pb, Zn, Cd and Cr,
based on the linear regression of deeper sediments (pre-
industrial). Aluminum is a better geochemical normalizer
than Fe and it is commonly used to describe the natural
metal variability of the coastal sediments. The evident
enrichment of Zn and Cd is recorded in the surface sedi-
ments of the eastern side of the Guangxi coast and the
central part of the Qinzhou Bay, but it does not exceed the
effects range-low values, due to a low percentage of fine-
grained sediments in the region. Although the Pb and Cr
concentrations are mainly of natural origin, 3 and 6% sites
exceed the effects range-low values, respectively; indicat-
ing the potential for adverse ecological effects of metals on
the benthic communities.
Keywords Heavy metals � Coastal sediments �Background levels � Linear regression � Contamination �Beibu Gulf
Introduction
Heavy metals, originated from both natural and anthropo-
genic sources, are continuously introduced to the estuarine
and the coastal sediments, commonly acting as sinks of
river borne metals, which may cause significant and per-
manent disturbances in the coastal systems (Angelidis and
Aloupi 1997; Dassenakis et al. 1996; Jha et al. 2003).
Based on the metal concentrations alone, it is therefore
difficult to distinguish the natural from the anthropogenic
sources due to the differences of the grain-size distribution
and the mineralogical composition in these sediments
(Loring 1991; Roussiez et al. 2005). It is desirable, there-
fore, to establish both background metal concentrations and
their natural variability prior to assessing human impacts
(Veinott et al. 2001).
For these reasons, linear regression based on deep sed-
iments (e.g., pre-industrial) can provide a more meaningful
basis for the regional background levels (Aloupi and
Angelidis 2001a; Covelli and Fontolan 1997; Doherty et al.
2000; Loring 1991; Roussiez et al. 2005; Schropp et al.
1990; Summers et al. 1996; Veinott et al. 2001), assuming
that early diagenetic processes did not alter the vertical
distribution of the considered element (Blaser et al. 2000;
Szefer et al. 1995; Veinott et al. 2001). If surface sediments
have concentrations of metals that are statistically higher
than those of deeper sediments, the metal enrichment is
suggested (Alexander et al. 1993; Baptista Neto et al. 2000;
Summers et al. 1996).
The coastal zone of Guangxi province is not only an
important Mangrove/Wetland Reserve but also a shellfish
culture area. On its northern shores are located the cities of
Beihai, Qinzhou and Fangcheng, where the quantity of coal
and petroleum consumption increased rapidly from
4.2 9 106 to 2.8 9 107 ton and from 1.8 9 105 to
P. Xia (&) � X. Meng � A. Feng � J. Zhang � X. Wang
First Institute of Oceanography,
State Oceanic Administration, Qingdao 266061, China
e-mail: [email protected]
X. Meng
e-mail: [email protected]
A. Feng
e-mail: [email protected]
P. Yin
Qingdao Institute of Marine Geology,
China Geological Survey, Qingdao 266071, China
123
Environ Earth Sci (2012) 66:1337–1344
DOI 10.1007/s12665-011-1343-y
1.4 9 106 ton (Chen et al. 1997) during 1990–2006,
respectively. Therefore, the metals that derived from the
fossil fuel combustion, the urban/industrial sewage and
runoff have markedly increased and are still continuing,
which may be causing significant and permanent distur-
bances in the coastal systems. However, except for
research about ecological, chemical, sedimentological
characteristics (Li 2004; Liang and Li 2002; Wen et al.
2002; Xia et al. 2008; Zheng et al. 1995), few other studies
on this field have been carried out, and even fewer on the
metal concentrations and their distribution in the surface
sediments along the coastal zone. The principal aim of this
paper is (1) to choose the most suitable normalizer for
establishing the regional background levels based on the
deeper sediments, (2) and to determine if there has been
any anthropogenic input of metals to the surface sediments.
Materials and methods
Sampling sites
The study area is located in the Guangxi coast, facing
Beibu Gulf and bordering Vietnam on the southwest. It has
a humid subtropical climate, with the average temperature
ranging between 17� and 22�. The coastline of Guangxi
runs for 1,628 km, along which the beach area is 1,005,
and 1,438 km2 in shallow waters within the depth of 5 m
(Song 2009). There are 56.54 km2 of mangrove habitat
(40% of China’s total) and large deposits of titanium,
quartz sands and xenotime. In the shallow sea, there are
more than 50 economic fish species and 10-odd commer-
cial shrimp species.
One hundred surface sediment samples (0–2 cm) and
four sediment cores (80–86 cm long) were collected during
2006–2007 from the intertidal zone of Guangxi province
(SW China; Fig. 1). To minimize any disturbance during
sampling, the sediment cores were carefully obtained using
10 cm diameter PVC tubes. The cores were extruded using
a manually driven piston, and were sliced using stainless
steel cutters at 2 cm intervals. After collection, the subs-
amples were sealed with polyethylene bags and kept in 4�C
until analysis.
Laboratory analysis
The grain-size distribution was measured by wet sieving
and the following fractions were determined: silt ? clay
(\63 lm), sand (63 lm [ x [ 2 mm) and gravel
([2 mm). The major and trace element contents were all
determined in a fraction \2 mm. The total organic carbon
(TOC) concentrations were obtained by digesting *0.5 g
of dried sediment with potassium dichromate in a sulfuric
medium and titration of the excess of dichromate with
ferrous sulfate (Nelson and Sommers 1996).
Samples for element analysis were wind-dried at room
temperature, and then finely powdered in an agate mortar.
Approximately 0.2 g of the dried ground sediment was
totally digested in a mixture of 5:4:1 HNO3 ? HCl ? HF
using a microwave oven (Loring and Rantala 1992). The
residue was solubilized by HNO3 and diluted to volume.
The major (Al, Fe) and trace elements (Pb, Zn, Cd and Cr)
were analyzed by ICP-OES and ICP-MS, respectively. The
detection limits (lg g-1) were found to be 1,000 for Al and
Fe; 5 for Cr; 2 for Pb and Zn; and 0.03 for Cd. The quality
assurance of the analytical results was controlled with the
use of the standard reference materials (GSD9 Stream
Sediment, GBW07313 Marine Sediment), and the recov-
eries obtained from the above reference materials are
shown in Table 1.
Statistical methods
Based on the assumption that the natural metal concen-
trations should depict a high degree of correlation with the
normalizer element, the regional background levels can be
estimated by a linear regression from the data of the deeper
sediments (Roussiez et al. 2005).
The values for each metal were tested to determine if
they were normally distributed using a Kolmogorov–
Smirnov test (Roussiez et al. 2005; Veinott et al. 2001). In
the paper, all metals met the normality test (p \ 0.05), and
no-transformation (log- or inverse-) was performed. A 95%
prediction interval has been drawn for each regression
using Systat Sigmaplot 10. Then, all samples that were
standing outside the upper limit were eliminated and con-
sidered as anomalous or enhanced (Doherty et al. 2000).
After each elimination step, the least-squares regression
was recalculated. This process was repeated until no
sample fell outside the upper limit, after that the solid line
represents the regional background levels with the slope-
intercept form. Finally, data from the recent sediments
were compared to the old sediments and examined for
evidence of metal enrichment by anthropogenic inputs.
Results and discussion
Regional background levels
The contents of Al, Fe, TOC and silt ? clay (S ? C) in the
cores are presented in Fig. 2a–d, and the fine-grained
fraction (S ? C) is more abundant in core Q32 and F14
(65.99 ± 22.85 and 59.92 ± 15.15%, respectively) than in
cores Q24 and O18 (45.97 ± 24.44 and 39.94 ± 13.09%,
respectively). They also have a great granulometric
1338 Environ Earth Sci (2012) 66:1337–1344
123
variability, varying from fine-grained material (1.67%
S ? C, 51 cm of core Q24) to sandy sediments (97.98%
S ? C, 75 cm of core F14). Similar patterns in the distri-
bution of Al, Fe, TOC and metals are also found in the
cores. Based on 210Pb dating using the CIC model, the
sedimentation rates of the cores ranged from 0.25 to
1.68 cm year-1 (as yet unpublished). Then, the deeper
sediments below 50 cm would be at least 30 years old and
probably much older (e.g., 1679–1807 AD in core Q24,
corresponding to the pre-industrial), when the anthropo-
genic activities in the Guangxi shore and its adjacent area
were very scarce (Song 2009).
The down-core variations of metals are showed in
Fig. 2e–h, and its concentrations along the cores are in the
range 3.97–108.12 lg g-1 for Pb, 8.93–88.83 lg g-1 for
Zn, 0.02–0.17 lg g-1 for Cd and 10.71–70.67 lg g-1 for
Cr. Maximal concentrations of Pb, Zn, Cd and Cr were
generally obtained in the surface layers (\10 cm) of cores
Q24 and F14, then, showing a decreasing trend with depth.
This general pattern is not observed for the bottom layers
(\40 cm) in core Q32, where metal concentrations are at
least two times higher than on the surface. The differences
in the metal concentrations, particularly in core Q32, are
greatly due to the lithological differences. Without some
normalization procedure, it could be interpreted as an
enrichment or contamination in the deeper sediments of
core Q32.
The raw data are not sufficient to quantify the intensity
of contamination in the sediment layers. Normalization to a
conservative element is a common procedure used for the
detection and the quantification of anomalous metal con-
centrations, based on the main assumption that the exis-
tence of a linear relationship between the normalizers (e.g.,
Al, Fe, Li, Cs, Sc and TOC) and the fine-grained fractions
in the ‘‘natural’’ sediments. Among these potential nor-
malizers, Al and Fe have been the most frequently used in
the estuarine and coastal studies (Roussiez et al. 2005;
Schiff and Weisberg 1999), while Li, Cs, Sc and TOC are
more unusual and were used to a lesser extent.
Table 2 presents the affinities of the potential normalizers
with the studied metals and the fine-grained fractions. A subset
of 61 deeper sediment samples was used, including the core
F14 (50–80 cm, N = 15), O18 (50–84 cm, N = 17), Q24
(60–82 cm, N = 11) and Q32 (50–86 cm, N = 18). A strong
positive correlation between elements and the S ? C was
found (0.76 \ r\0.82, P \ 0.001; Table 2), implying that
the major and trace elements are associated with the fine-
grained fractions in the study area. Furthermore, the strong
positive correlation between metals and Al, Fe (0.90 \ r \0.99, P \ 0.001) suggest either their common accumulation
in the fine-grained aluminosilicate materials, and/or as a
geochemical substrate for metals. Nevertheless, non-correla-
tion of TOC with the S ? C and all the metals (-0.15\ r\0.12, P [ 0.05) indicate that the distributions of TOC
(1.28 ± 0.23%) do not significantly affect the pattern of the
metal distributions in the sediments.
Compared to the other candidates, Al depicts the higher
correlation both with the S ? C (r = 0.86) and with the
metals (r [ 0.93) investigated. Moreover, Al is the major
constituent of the fine-grained aluminosilicates with which
the bulk of heavy metals is associated and insensitive to the
anthropogenic sources. These indicate that Al is the most
suitable element for the normalization procedure in the
study area. Also, Fe may be an alternative choice, since this
element has a similar behaviour as Al in our samples.
108.0° 108.2° 108.4° 108.6° 108.8° 109.0° 109.2° 109.4° 109.6°
21.2°
21.4°
21.6°
21.8°
22.0°
22.2°
Nanliu River
Dafeng Rive
r
Qin
jiang
Rive
r
Maoling River
Fangcheng River
Beihai
Qinzhou
Fangcheng
E
N
F14
O18
Q24
Q32
Beibu Gulf
Guangxi province
(b)
China
(c)
(a)Cores
Surface
intertidal zone
depth contours
10 m
20 m
Fig. 1 Location of a the samples collected from the intertidal zone of b Guangxi, c China
Table 1 Metal concentration recoveries (%) from reference materials
Element Al Fe Pb Zn Cd Cr
GSD9 102.6 99.9 97.9 99.0 101.9 99.3
GBW07313 97.0 98.2 99.3 95.2 –a 99.0
a Not certified
Environ Earth Sci (2012) 66:1337–1344 1339
123
The Metal/Al ratios show a net increase in the upper
sediments, indicating an evidence of human disturbance,
which can be detected up to the depth of 10 cm for Pb (core
F14) and to the depth of 30 cm for Zn, Cd and Cr (core
Q32). A similar but weaker anthropogenic impact is also
apparent in the core O18 and Q24, suggesting that the
excess metal concentrations in the upper layers should be
attributed to anthropogenic inputs. On the other hand, all
the metals (Fig. 2i–l) showed relatively stable Metal/Al
ratios below 50 cm depth, with the exception of core Q24
(a)
(e)
(b) (c) (d)
(f) (g) (h)
(i) (j) (k) (l)
Fig. 2 Vertical profiles of Al, Fe, TOC, silt ? clay, metals (Pb, Zn, Cd and Cr) and Metal/Al ratios in the sediment cores
Table 2 Pearson correlation matrix of potential normalizers and
heavy metals in the deeper sediments (N = 61)
Normalizer S ? C Pb Zn Cd Cr
Al 0.82** 0.99** 0.99** 0.93** 0.95**
Fe 0.76** 0.98** 0.98** 0.90** 0.92**
TOC 0.12* -0.06* -0.02* 0.08* -0.15*
S ? C 1.00 0.79** 0.81** 0.78** 0.76**
* Non-significant (P [ 0.05)
** Correlation is all significant at the 0.01 level (two-tailed)
1340 Environ Earth Sci (2012) 66:1337–1344
123
at the depth of 49–59 cm, which showed an evident dis-
turbance similar to that of the S ? C at the same depth. It
should be attributed to the deposition of coarse-grained
resuspended sediments, which diluted the S ? C content to
1.66–7.90%, related to the excessive quarrying of sand on
the Qinjiang riverbed (Lang et al. 2007).
With the exception of the disturbance (Fig. 2i–l), any
difference in metal concentrations of deeper sediments
between cores could be a result of natural variability (Loring
1991). It has been a successfully met the assumption,
because the deeper sediments (below 50 cm) were free of
any metal inputs derived from human activities in the region.
The Scatter plots of linear regression models between Al
and the metals are presented in Fig. 3. A few anomalous
points of Pb, Cr, Hg and As (5, 3, 8 and 4, respectively) fall
outside the 95% prediction intervals, but they are all near
the prediction lines. An examination of the raw data indi-
cated nothing unusual for these points other than natural
variability. For the samples from the model suite, the
coefficient of determination (R2) of metals with Al is
greater than 0.93 and is linear for all metals. The param-
eters and characteristics of the regional background levels
(solid lines, Fig. 3) are showed in Table 3.
Surface metal enrichment
A wide range of values for metal concentrations is
observed in the surface sediments of the Guangxi coast
(Table 4). In order to distinguish natural and anthropogenic
inputs, it was more useful to calculate the non-dimensional
enrichment factor (EF) by normalizing the metal concen-
trations to Al (Balachandran et al. 2005; Covelli and
Fontolan 1997).
For a given heavy metal, EF is calculated as follows
(Rule 1986):
EF ¼ Me/Alð Þsample= Me/Alð Þbackground;
where (Me/Al)Sample is the metal to Al ratio in the samples
of interest, (Me/Al)Background is the natural background
value of the metal to Al ratio. This general method has
been used in a number of research works (Audry et al.
2004; Grant and Middleton 1990; Ruiz-Fernandez et al.
2007; Rule 1986; Xia et al. 2011), although based on dif-
ferent normalizing elements and methods of background
determination. If an EF value is between 0.5 and 1.5 (i.e.,
0.5 B EF B 1.5), it is suggesting that the metal may be
entirely from crustal materials or natural weathering pro-
cesses (Zhang and Liu 2002). However, if an EF value is
greater than 1.5 (i.e., 1.5 \ EF), it is suggesting that a
significant portion of the metal is closely associated with
anthropogenic inputs.
The scatter plots of Pb, Zn, Cd and Cr to Al for the
surface sediments are presented in Fig. 4, and each dia-
gram shows the regression line (background levels,
Table 3) with the 95% prediction interval. According to the
EF values (Table 4), two main groups have been identified:
(1) Pb and Cr. Their data points are mostly located below
the dotted line of EF = 1.5 (Fig. 4a, d), indicating that they
(b)
(d)(c)
(a)Fig. 3 Determination of
regional background levels for
Pb, Zn, Cd and Cr based on their
correlation with Al (n = 61).
The dashed lines represent
prediction interval at the 95%
confidence level
Table 3 Characteristics of regression equations from the deeper
sediments (n = 61, Al %)
Metals
(mg/kg)
R2 N SE Regression equation
Pb 0.98 56 (5) 1.51 [Pb] = 3.55 [Al] ? 3.16
Zn 0.96 58 (3) 4.17 [Zn] = 6.78 [Al] ? 7.84
Cd 0.93 53 (8) 0.009 [Cd] = 0.0095 [Al] ? 0.026
Cr 0.98 57 (4) 1.97 [Cr] = 4.72 [Al] ? 12.83
(x) Number of anomalous samples removed from the regressions
Environ Earth Sci (2012) 66:1337–1344 1341
123
are mainly caused by the land-based natural inputs from the
erosion products. A few anomalous points of Pb (16) and
Cr (6) fall outside the 95% prediction intervals with the
maximum EF values of 4.66 and 3.40, respectively.
However, most of them are close to the dotted line,
showing that they are mainly of natural origin; (2) Zn and
Cd. Since 40 and 57 samples are enhanced (EF [ 1.5,
Fig. 4b, c) with maximum EF values of 7.45 for Zn and
21.08 for Cd, implying that both metals are mostly of
anthropogenic inputs.
The spatial distributions of the enhanced (EF [ 1.5)
metal concentrations are predominantly located on the
eastern side of Guangxi coast and in the central part of the
Qinzhou Bay (Fig. 5). It is not surprising that Zn and Cd
concentrations are markedly enhanced at these stations of
the eastern coast, especially near the mouth of Nanliu
River, due to some anthropogenic (domestic ? industrial)
inputs from the city of Beihai (1.5 million population) to
the intertidal zone by the river (Xia et al. 2008). Despite the
large number of enhanced stations existed, the enhanced
metal concentrations (Zn and Cd) do not exceed the effects
range-low (ERL) values at any station (Fig. 4b, c), indi-
cating that its potential risk of toxicity is still lower (Long
et al. 1995). The reason for this is that the metal-rich clay
minerals (Al, 2.05 ± 2.02%) will be carried away from the
shore into the deeper-shelf environments by strong tidal
currents and wave action (Doherty et al. 2000).
The three and six sites of Pb and Cr (respectively) is
slightly higher than ERL values (Fig. 4a, d), indicating
the potential for adverse ecological effects of metals on
the local benthic communities (Long et al. 1995). The
maximum Pb concentration (65.98 lg g-1) is found in
the central part of the Qinzhou Bay, only 4 km far from
the Qinzhou Port. The atmospheric transport of Pb from
the combustion of leaded gasoline (fishing boats and
cargo ships) is one of the main pollution pathways to the
adjacent surface sediments ( Aloupi and Angelidis
2001b). Furthermore, the abundance of fine-grained
fractions in the semi-closed harbor region (Fig. 5a) is apt
to absorb the metals in the water column (Loring 1991;
Summers et al. 1996). The enhanced Cr concentrations
(Fig. 5d) are mainly located in the mouths of Maoling
River and Dafeng River, indicating that river inputs are
an important local source of chromium pollution. This
may be derived from either mining or industrial activities
in the catchment areas.
Table 4 Metal concentrations (lg g-1) and enrichment factor (EF) in the surface sediments; ERL and ERM guideline values (lg g-1) and the
percent incidence of biological effects in the concentration ranges defined by the two values (Long et al. 1995)
Element Concentrations EF Guidelines Percent incidence of effects
Mean ± SD Range Mean ± SD Range ERL ERM \ERL ERL–ERM [ERM
Pb 18.34 ± 12.97 1.90–65.98 1.22 ± 0.50 0.53–4.66 46.7 218 97 3 0
Zn 52.63 ± 24.33 5.86–98.91 2.23 ± 1.71 0.68–7.45 150 410 100 0 0
Cd 0.14 ± 0.11 0.01–0.59 2.71 ± 2.89 0.41–21.08 1.2 9.6 100 0 0
Cr 33.23 ± 23.94 3.79–129.71 1.10 ± 0.53 0.28–3.40 81 370 94 6 0
(b)
(d)(c)
(a)Fig. 4 Metal Al scatter plot for
the surface sediments of
Guangxi coast. Solid linerepresents the regression line
based on deeper sediments
(background), dashed linesdefine the 95% prediction
interval, dotted line delineates
the boundary between the
natural and the enhanced
concentrations
1342 Environ Earth Sci (2012) 66:1337–1344
123
Conclusions
The paper provides key information to establish accurate
background levels for Pb, Zn, Cd and Cr in the coastal
sediments of the northern Beibu Gulf (SW China), based
on the linear regression of deeper sediments (pre-indus-
trial). It has successfully met the assumptions that the
deeper sediments were free of regional metal inputs
derived from human activities. Aluminum was better
suited than Fe for such normalization to accurately
describe the natural metal variability of the coastal sedi-
ments. Any difference in the metal concentrations of the
deeper sediments could be a result of natural variability
(similar metal/Al ratios), with the exception of core Q24
at the depth of 49–59 cm. It should be attributed to the
deposition of more coarse-grained sediments, related to
the excessive quarrying of sand on the Qinjiang riverbed
in the past.
In the surface sediments, Zn and Cd are mostly associ-
ated with the presence of anthropogenic inputs (EF [ 1.5),
but do not exceed the effects range-low values at any sta-
tions, due to a low percentage of fine-grained sediments in
the region. Although the Pb and Cr concentrations are
mainly derived from natural inputs (EF \ 1.5), 3 and 6%
of the sites (respectively) exceed effects range-low values,
indicating the potential for adverse ecological effects of
metals on the benthic communities. The enhanced stations
are mainly located on the eastern side of Guangxi coast and
in the central part of the Qinzhou Bay, which should be
attributed to differential discharge of untreated effluents
originating from the industrial and urban sources as well as
from combustion of leaded gasoline along with the fishing
and cargo activities.
Acknowledgments The authors thank Drs L. J. Liu, M. Z. Fu (First
Institute of Oceanography, SOA) and X. M. Dong for their great help
in the core sampling and laboratory analysis, and Ms. Lenka Sche-
uterova (Czech Republic) for her help in improving the English of the
manuscript. Thanks to two anonymous reviewers for their detailed
and constructive comments. This work was supported by the National
Basic Research Program of China (973 Program) under grant
No.2010CB951203; National 908 Program under grant No.GX908
(supplement).
References
Alexander CR, Smith RG, Calder FD, Schropp SJ, Windom HL
(1993) The historical record of metal enrichment in two Florida
estuaries. Estuaries 16:627–637
108.0° 108.2° 108.4° 108.6° 108.8° 109.0° 109.2° 109.4° 109.6°
21.2°
21.4°
21.6°
21.8°
22.0°
22.2°
NanliuRiver
Dafeng River
Qin
jiang
River
Maoling River
Fangcheng River
Beihai
Qinzhou
Fangcheng
E
N
Beibu Gulf
10 m
20 m
108.0° 108.2° 108.4° 108.6° 108.8° 109.0° 109.2° 109.4° 109.6°
21.2°
21.4°
21.6°
21.8°
22.0°
22.2°
NanliuRiver
Dafeng River
Qin
jiang
River
Maoling River
Fangcheng River
Beihai
Qinzhou
Fangcheng
E
N
Beibu Gulf
10 m
20 m
108.0° 108.2° 108.4° 108.6° 108.8° 109.0° 109.2° 109.4° 109.6°
21.2°
21.4°
21.6°
21.8°
22.0°
22.2°
NanliuRiver
Dafeng River
Qin
jiang
River
Maoling River
Fangcheng River
Beihai
Qinzhou
Fangcheng
E
N
Beibu Gulf
10 m
20 m
108.0° 108.2° 108.4° 108.6° 108.8° 109.0° 109.2° 109.4° 109.6°
21.2°
21.4°
21.6°
21.8°
22.0°
22.2°
NanliuRiver
Dafeng River
Qin
jiang
River
Maoling River
Fangcheng River
Beihai
Qinzhou
Fangcheng
E
N
Beibu Gulf
10 m
20 m
(b)
(c) (d)
QinzhouBay
QinzhouBay
QinzhouBay
QinzhouBay
(a)
(0, 1.5)EFSymbol
[1.5, 5)[5, 20)[20, 40)
EFSymbol
Fig. 5 Spatial distributions of enhanced metal concentrations in the surface sediments: a Pb; b Zn; c Cd and d Cr
Environ Earth Sci (2012) 66:1337–1344 1343
123
Aloupi M, Angelidis MO (2001a) Geochemistry of natural and
anthropogenic metals in the coastal sediments of the island of
Lesvos, Aegean Sea. Environ Pollut 113:211–219
Aloupi M, Angelidis MO (2001b) Normalization to lithium for the
assessment of metal contamination in coastal sediment cores
from the Aegean Sea, Greece. Mar Environ Res 52:1–12
Angelidis MO, Aloupi M (1997) Assessment of metal contamination
in shallow coastal sediments around Mytilene Greece. Int J
Environ Anal Chem 68(2):281–293
Audry S, Schafer J, Blanc G, Jouanneau JM (2004) Fifty-year
sedimentary record of heavy metal pollution (Cd, Zn, Cu, Pb) in
the Lot River reservoirs (France). Environ Pollut 132:413–426
Balachandran KK, Lalu Raj CM, Nair M, Joseph T, Sheeba P, Venugopal
P (2005) Heavy metal accumulation in a flow restricted, tropical
estuary. Estuar Coast Shelf Sci 65(1–2):361–370
Baptista Neto JA, Smith BJ, McAllister JJ (2000) Heavy metal
concentrations in surface sediments in a nearshore environment,
Jurujuba Sound, Southeast Brazil. Environ Pollut 109:1–9
Blaser P, Zimmermann S, Luster J, Shotyk W (2000) Critical
examination of trace element enrichments and depletions in
soils: As, Cr, Cu, Ni, Pb, and Zn in Swiss forest soils. Sci Total
Environ 249:257–280
Chen RQ, Cao CC, Ruan GH (1997) Invariable element geochemistry
of coals in Guangxi. Coal Geol China 9(2):40–44 (in Chinese
with English abstract)
Covelli S, Fontolan G (1997) Application of a normalization
procedure in determining regional geochemical baselines. Envi-
ron Geol 30(1/2):34–45
Dassenakis MI, Kloukiniotou MA, Pavlidou AS (1996) The influence
of long existing pollution on trace metal levels in a small tidal
Mediterranean Bay. Mar Pollut Bull 32(3):275–282
Doherty GB, Brunskill GJ, Riddm J (2000) Natural and enhanced
concentrations of trace metals in sediments of Cleveland Bay, Great
Barrier Reef Lagoon, Australia. Mar Pollut Bull 41:337–344
Grant A, Middleton R (1990) An assessment of metal contamination
of sediments in the Humber Estuary, UK. Estuar Coast Shelf Sci
31:71–85
Jha SK, Chavan SB, Pandit GG, Sadasivan S (2003) Geochronology
of Pb and Hg pollution in a coastal marine environment using
global fallout 137Cs. J Environ Radioact 69:145–157
Lang YS, Li JW, Deng XD, Zhang W, Yan DR, Chen L (2007)
Mineralogy and geochemistry of supergene manganese ore
deposits in Qinzhou-Fangcheng area, southern Guangxi, with
implications for ore genesis. Miner Depos 26(5):527–540 (in
Chinese with English abstract)
Li C (2004) Quantitative distribution of mangroves in Guangxi
Zhuang Autonomous Region. J Beijing For Univ 26:47–52 (in
Chinese with English abstract)
Liang W, Li G (2002) Discussion on the modern sedimentary of
mangrove coasts in Guangxi. J Guangxi Acad Sci 18(3):131–134
(in Chinese with English abstract)
Long ER, Macdonald DD, Smith SL, Calder FD (1995) Incidence of
adverse biological effects within ranges of chemical concentra-
tions in marine and estuarine sediments. Environ Manag
19:81–97
Loring DH (1991) Normalization of heavy-metal data from estuarine
and coastal sediments. ICES J Mar Sci 48:101–115
Loring DH, Rantala RTT (1992) Geochemical analyses of marine
sediments and suspended particulate matter. Technical Report,
Fisheries and Marine Service 700, p 58
Nelson DW, Sommers LE (1996) Total carbon, organic carbon, and
organic matter. In: Sparks DL et al (eds) Methods of soil
analysis. Part 3-Chemical methods. Soil Sci Soc Am, Madison,
pp 961–1010
Roussiez V, Ludwig W, Probst JL, Monaco A (2005) Background
levels of heavy metals in surficial sediments of the Gulf of Lions
(NW Mediterranean): an approach based on 133Cs normalization
and lead isotope measurements. Environ Pollut 138:167–177
Ruiz-Fernandez AC, Hillaire-Marcel C, Paez-Osuna F (2007) 210Pb
chronology and trace metal geochemistry at Los Tuxtlas,
Mexico, as evidenced by a sedimentary record from the Lago
Verde Crater Lake. Quart Res 67:181–192
Rule JH (1986) Assessment of trace element geochemistry of
Hampton Roads Harbor and Lower Chesapeake Bay area
sediments. Environ Geol Water Sci 8:209–219
Schiff KC, Weisberg SB (1999) Iron as a reference element for
determining trace metal enrichment in Southern California
coastal shelf sediments. Mar Environ Res 48:161–176
Schropp SJ, Lewis FG, Windom HL, Ryand JD, Calder FD, Burney
LC (1990) Interpretation of metal concentrations in estuarine
sediments of Florida using aluminium as a reference element.
Estuaries 13:227–235
Song JF (2009) Estimate the rationality of spatial structure of Beibu
Gulf (Guangxi) economic zone and analyze the agglomeration
trend. Int J Bus Manag 4(1):132–137 (in Chinese with English
abstract)
Summers JK, Wade TL, Engle VD, Malaeb ZA (1996) Normalization
of metal concent rations in estuarine sediments from the Gulf of
Mexico. Estuaries 19(3):581–594
Szefer P, Kusak A, Szefer K, Jankowska H, Wolowicz M, Ali AA
(1995) Distribution of selected metals in sediments cores of Puck
Bay, Baltic Sea. Mar Pollut Bull 40:615–618
Veinott G, Perron-cashman S, Anderson MR (2001) Baseline metal
concentrations in coastal Labrador sediments. Mar Pollut Bull
42(3):182–192
Wen Y, Liu S, Yuan C (2002) The population distribution of
mangrove at Yingluogang of Guangxi, China. Acta Ecol Sin
22(7):1160–1165 (in Chinese with English abstract)
Xia P, Meng XW, Yin P, Liu LJ (2008) Heavy metal pollution and its
potential ecological risk in the sediments from the Beihai
intertidal zone of Guangxi province. Adv Mar Sci 26(4):471–477
(in Chinese with English abstract)
Xia P, Meng XW, Yin P, Cao ZM, Wang XQ (2011) Eighty-year
sedimentary record of heavy metal inputs in the intertidal
sediments from the Nanliu River estuary, Beibu Gulf of South
China Sea. Environ Pollut 159(1):92–99
Zhang J, Liu CL (2002) Riverine composition and estuarine
geochemistry of particulate metals in China-weathering features,
anthropogenic impact and chemical fluxes. Estuar Coast Shelf
Sci 54:1051–1070
Zheng W, Lin P, Xue X, Lu C, Zheng F, Yin Y (1995) Dynamics of
carbon, hydrogen and nitrogen elements in Rhizophora stylosamangrove community at Yinluo Bay of Guangxi, China. Chin J
Appl Ecol 6(1):17–22
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